* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: With sodium periodate; sulfuric acid; iodine In ethanol at 65℃; for 1 h; Stage #2: With sodium hydroxide In ethanol
To an ethanol solution (500 mL) of carbazole (2.50 g, 15.0 mmol), NaIO4 (0.80 g, 3.75 mmol) and I2 (1.89 g, 7.45 mmol) were added in this order, and then an ethanol solution (100 mL) of H2SO4 (1.60 mL, 30.0 mmol) was added thereto. The reaction solution was heated to reflux for one hour at 65°C. Disappearance of the raw materials was confirmed by TLC (HexH:AcOEt = 4:1), and an ethanol solution (100 mL) of NaOH (1.4 g) was added thereto to neutralize the reaction solution. Ethanol was removed, and then the reaction solution was extracted two times with chloroform and washed two times with water. The organic phase was dried over Na2SO4, and the solvent was removed. The residue was purified by column chromatography (HexH:AcOEt = 4:1), and compound (1) (3.06g, 70percent) was obtained as a white powder. Thus, 3,6-diiodocarbazole (0.47 g, 7.5percent) was obtained as a white powder. 1: 1H NMR (DMSO-d6) 5 11.4 (s, 1H), 8.49 (d, 1H, J = 1.7 Hz), 8.14 (d, 1H, J = 8.0 Hz), 7.62 (dd, 1H, J = 8.4, 1.7 Hz), 7.48 (d, 1H, J = 8.0 Hz), 7.40 (m, 1H), 7.33 (d, 2H, J = 8.4 Hz), 7.16 (m, 1H). 3,6-Diiodocarbazole: 1H NMR (DMSO-d6) δ 11.5 (s, 1H), 8.56 (d, 2H, J = 1.7 Hz), 7.65 (dd, 2H, J = 8.5, 1.7 Hz), 7.34 (d, 2H, J = 8.5 Hz).
70%
Stage #1: With sodium periodate; sulfuric acid; iodine In ethanol at 65℃; for 1 h; Stage #2: With sodium hydroxide In ethanol
To an ethanol solution (500 mL) of carbazole (2.50 g, 15.0 mmol), NaIO4 (0.80 g, 3.75 mmol) and I2 (1.89 g, 7.45 mmol) were sequentially added, and then an ethanol solution (100 mL) of H2SO4 (1.60 mL, 30.0 mmol) was added. The reaction solution was refluxed for one hour at 65° C. The loss of raw materials was confirmed by TLC (HexH:AcOEt=4:1), and an ethanol solution (100 mL) of NaOH (1.4 g) was added thereto to neutralize the system. Ethanol was removed, and then the reaction solution was extracted two times with chloroform. The extract was washed two times with water. The organic phase was dried over Na2SO4, and the solvent was removed. The residue was purified by column chromatography (HexH:AcOEt=4:1), and thus compound 1 (3.06 g, 70percent) was obtained as a white powder. Thus, 3,6-diiodocarbazole (0.47 g, 7.5percent) was obtained as a white powder.1: 1H NMR (DMSO-d6) δ 11.4 (s, 1H), 8.49 (d, 1H, J=1.7 Hz), 8.14 (d, 1H, J=8.0 Hz), 7.62 (dd, 1H, J=8.4, 1.7 Hz), 7.48 (d, 1H, J=8.0 Hz), 7.40 (m, 1H), 7.33 (d, 2H, J=8.4 Hz), 7.16 (m, 1H).3,6-Diiodocarbazole: 1H NMR (DMSO-d6) δ 11.5 (s, 1H), 8.56 (d, 2H, J=1.7 Hz), 7.65 (dd, 2H, J=8.5, 1.7 Hz), 7.34 (d, 2H, J=8.5 Hz).
Reference：
[1] Patent: EP2216338, 2010, A1, . Location in patent: Page/Page column 10
[2] Patent: US2011/34683, 2011, A1, . Location in patent: Page/Page column 9; 10
[3] Journal of Organic Chemistry, 2015, vol. 80, # 4, p. 2392 - 2396
[4] Journal of Organic Chemistry, 2011, vol. 76, # 14, p. 5685 - 5695
[5] Journal of the Chemical Society, 1926, p. 549
[6] Tetrahedron Letters, 2006, vol. 47, # 39, p. 6957 - 6960
[7] Dyes and Pigments, 2017, vol. 137, p. 24 - 35
[8] Journal of Materials Chemistry C, 2017, vol. 5, # 38, p. 9854 - 9864
[9] Dyes and Pigments, 2018, vol. 159, p. 173 - 178
2
[ 86-74-8 ]
[ 16807-13-9 ]
[ 57103-02-3 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
3
[ 86-74-8 ]
[ 16807-13-9 ]
[ 57103-02-3 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
[2] Russian Journal of Organic Chemistry, 2003, vol. 39, # 6, p. 875 - 880
4
[ 86-74-8 ]
[ 57103-02-3 ]
Yield
Reaction Conditions
Operation in experiment
96%
Stage #1: With trifluorormethanesulfonic acid; [bis(pyridine)iodine]+ tetrafluoroborate In dichloromethane at 0 - 20℃; for 20 h; Stage #2: With sodium thiosulfate In dichloromethane
A mixture of 278 mg (0.75 mmol, 2.5 eq.) of bis(pyridine)iodonium tetrafluoroborate (IPy2BF4) and 50 mg (0.30 mmol) of carbazole was added with 8 mL of dichloromethane under a nitrogen atmosphere, and further added dropwise with 26.4 μl (0.30 mmol, 1 eq.) of trifluoromethanesulfonic acid (TfOH) under a temperature condition of 0° C. Then, the resultant mixture was stirred under a nitrogen atmosphere at room temperature for 20 hours to obtain an orange-yellow reaction mixture (I). Subsequently, an excessive iodization reagent in the orange-yellow reaction mixture (I) thus obtained was decomposed with sodium thiosulfate (Na2S2O3). Thereafter, the aqueous layer was extracted with dichloromethane. After that, the collected organic phase was washed with sodium chloride, dried with sodium sulfate (Na2SO4), filtered, and concentrated to obtain a crude product (I) (136.9 mg). Then, the crude product (I) thus obtained was separated and purified by silica gel chromatography (hexane:EtOAc=5:1). Thereby, 3,6-diiodocarbazole expressed by the following general formula (94) was obtained (a yield of 120.1 mg and 96percent). The 3,6-diiodocarbazole thus obtained was subjected to 13C NMR and 1H NMR measurements. FIG. 63 shows a graph obtained from the 13C NMR measurement, and FIGS. 64 and 65 show graphs obtained from the 1H-NMR measurements. These obtained results are shown below.1H NMR (CDCl3) 8.32 (d, J=1.9 Hz, 2H), 8.09 (br, 1H), 7.68 (dd, J=8.4 Hz, 1.9 Hz, 2H), 7.22 (d, J=8.4 Hz, 2H);13C NMR (CDCl3) 138.34, 134.68, 129.26, 124.44, 112.63, 82.41.
90%
at 80℃;
A mixture of carbazole (24 g, 144 mmol) and acetic acid (360 mL) was heated to 80 °C, and then finely-crushed potassium iodide (31 .5 g, 1 89 mmol) was added. After a few minutes of stirring, potassium iodate (24 g, 100 mmol) was carefully added in small increments, and the system was maintained at 80 °C until the resulting iodine was fully consumed. The mixture was cooled to 40 °C and filtered, followed by washing with 30 mL acetic acid, 1 00 mL methanol and water sequentially, resulting in 51 g yellow solid of 3,6-Diiodo-9H-carbazole. Yield: 90percent. NMR (300 MHz, CDC13, δ): 8.33 (m, 2H), 8.15 (m, 1 H), 7.70-7.60 (m, 2H), 7.23-7.20 (m, 2H).
84%
With potassium iodate; potassium iodide In acetic acid for 1 h; Reflux
To a mixture of carbazole (16.72 g, 0.1 mol) and KI (21.58 g, 0.13 mol) was added with 280 mL glacial acetic acid. After heating to reflux to dissolve all the solids in glacial acetic acid, the mixture was cooled down and added with ground potassium iodate (32.1 g,0.15 mol). Then, the reaction mixture was heated again to reflux for1 h and afterward cooled down to room temperature. A large amount of compound I-Cz was precipitated during the reaction.The crude product was separated by filtration and washed with water, affording pure I-Cz (35.24 g) as gray solid in yield of 84percent.
75%
at 80℃; for 5 h;
Potassium carbamate (6.0 g, (λ040 mol) and potassium iodide (6.0 g, (λ040 mol) and potassium iodide50 mL of glacial acetic acid was placed in a 100 mL round-bottomed flask; the reaction was stirred at 80 ° C in a water bath and stirred until the resulting iodineThe color disappeared (about 5 h); the mixture was then cooled and filtered through a Buchner funnel to give a solid crude product5percent (wtpercent) NaHSOj ^ aqueous solution to remove unreacted 12 and excess KI03; the crude product was dried and washed with ethanol /THF to recrystallize, decolorize with a small amount of activated charcoal, and finally give white crystals 9. 4 g; Yield: 75percent
66.7%
at 80℃;
Carbazole (8.36 g,50 mmol) was dissolved in boiling acetic acid (200 mL). To the solution, potassium iodide (10.8 g,50 mmol) was added. The solution was cooled and potassium iodate (21.5 g, 50 mmol) was added. The mixture was refluxed at 80°C for 1 h. The solution was decanted from undissolved potassium iodate and allowed to cool to room temperature. The crude product separated by filtration and recrystallized from dichloromethane to give brown solid (13.97 g, 66.7percent).1H NMR (CDCl3, 400 MHz): δ (ppm) = 8.36 (s, 2H),8.14 (br, s, 1H), 7.71 (dd, 2H, J = 8.50, 1.65 Hz), 7.24(d, 2H, J = 8.56 Hz). 13C NMR (CDCl3, 100 MHz):δ (ppm) = 138.53, 134.83, 129.40, 124.58, 112.70,82.44.
65%
With potassium iodate; acetic acid; potassium iodide In water at 80℃; for 48 h;
To a round bottom flask (250 mL, two-neck), equipped with a magnetic stir under atmosphere, was loading a solution of carbazole (15 g, 89.71 mmol), KI (19.36 g, 116.62 mmol), KIO3 (19.20 g，89.71 mmol), acetic acid (100 mL) and deionized water (10 mL). The iodination reaction was continued at 80 °C for 48 h. After cooling to room temperature, the mixture was filtered, washed with deionized water, saturated Na2CO3 solution, and methanol to afford a white powder 1 24.4 g, yield 65percent), m.p. 208-209 °C. 1H NMR (400 MHz, CDCl3): δ = 8.29 (s, 2H), 8.09 (br, 1H), 7.65 (d, 2H), 7.18 (d, 2H). ;13C NMR (100 MHz, CDCl3): δ = 138.52, 134.80, 129.37, 124.56, 112.68, 82.41. HRMS (m/z): calcd for C12H7I2N: 418.8668. Found: 418.8678.
63%
Stage #1: With potassium iodide In acetic acid at 50℃; Stage #2: With potassium iodate In acetic acid for 1 h; Reflux
Carbazole (1.00 g, 5.98 mmol) was dissolved into acetic acid (16 mL) and the solution was heated to 50 °C. Then finely-crushed KI (1.29 g, 7.77 mmol) was added. After a few minutes of stirring, KIO3 (1.279 g, 5.98 mmol) in acetic acid (2 mL) was added dropwise.The mixture was refluxed for 1 h to give a light red suspension. After cooling to room temperature, water was added and the mixture was extracted with CH2Cl2. The combined organic phase was washed with water, brine, dried over anhydrous MgSO4, filtered, and concentrated. Purification by recrystallization (ethyl acetate/petroleum ether) gave 1 as a red-brown powder (1.61 g, 63percent). 1H NMR (600 MHz, CDCl3): δ 8.32 (d, J 1.8 Hz, 2H), 8.10 (s,1 H), 7.68 (dd, J 8.4,1.8 Hz, 2H), 7.22 (d, J 8.4 Hz, 2H).
60%
With potassium iodate; potassium iodide In water; acetic acid at 80℃; for 48 h;
A solution containing 16.7 g (0.1 mol) of 9H-carbazole, 21.6 g (0.13 mol) of KI, 21.4 g (0.1 mol) of KIO3, 150 cm3 of acetic acid, and 15 cm3 of water was heated for 48 h on a water bath at 80 C. After cooling to the room temperature, the precipitate was filtered off and washed with water, saturated Na2CO3 solution, and methanol. The crude product was crystallized from toluene. The yield was 25 g of 3,6-diiodo-9H-carbazole
55%
With sodium periodate; sulfuric acid; iodine In ethanol at 65℃; for 3 h;
Example 4Synthesis of Compound 4; The following method was followed to synthesize the compound 4 of the following formula (XIV). Note that, when synthesizing the compound 4, this was synthesized by first obtaining the intermediate B which is shown by the following formula (XV), next obtaining the intermediate C which is shown by the following formula (XVI) from the obtained intermediate B, and finally oxidizing the obtained intermediate C. First, the following method was used to produce the intermediate B. That is, a two-necked reactor was charged with carbazole 25.0 g (149.5 mmol) and iodine 30.36 g (239.2 mmol), then these were made to dissolve in ethanol 600 ml. Next, to this solution, sodium periodate 12.8 g (59.80 mmol) was added. Further, concentrated sulfuric acid 1 g was slowly added dropwise, then the total volume was made to react at 65° C. for 3 hours. After that, the reaction solution was returned to room temperature, was concentrated by a rotary evaporator down to 150 ml or so, then the concentrated solution was charged with distilled water 500 ml and saturated sodium chloride solution 300 ml and the result was extracted by chloroform 1000 ml. The organic layer was made to dry over anhydrous sodium sulfate, was concentrated by a rotary evaporator, then the concentrate was charged with n-hexane to recrystallize it and thereby obtain the intermediate B in 34.4 g for a yield of 55percent. The structure of the obtained intermediate B was identified by 1H-NMR.1H-NMR (500 MHz, DMSO-d6, TMS, δppm): 7.35 (d, 2H, J=8.5 Hz), 7.66 (dd, 2H, J=8.5, 1.5 Hz), 8.57 (d, 2H, J=1.5 Hz), 11.54 (s, 1H).
18.79%
With potassium iodate; potassium iodide In acetic acid at 45℃;
Carbazole 1 (12.23 g, 73mmol) was dissolved in boiling glacial acetic acid (300 mL), and KI (15.84 g, 95mmol) was added. The solutionwas cooled, ground potassiumiodate (23.42 g, 150mmol)wasadded, and the mixture was then boiled until it acquireda clear straw-colored tint (10 min). The hot solution wasdecanted from the undissolved potassium iodate, and it wasallowed to cool to 45°C. The faintly brown plates were rapidlyfiltered off and recrystallized from alcohol, and the solutionwas allowed to cool to 45°C and filtered, yielding 5.75g of 8as a brown solid (18.79percent): mp 202°C (mplit. 202°C), 1HNMR(400MHz, CDCl3) δ ppm 8.34 (s, 2 H), 8.16 (br. s., 1 H), 7.70(dd, J = 8.53, 1.63Hz, 2 H), 7.23 (d, J = 8.41 Hz, 2 H); 13CNMR (100MHz, CDCl3) 138.5, 134.8, 129.4, 124.5, 112.7 and82.5. Maldi-Tof MS: m/z calcd for [M+] = C12H7I2N 418.867; found 418.868. Anal. calcd. for C12H7I2N: C, 34.40; H, 1.68; I,60.58; N, 3.34. Found: C, 34.38; H, 1.65; I, 60.55; N, 3.30.
18.79%
With potassium iodate; potassium iodide In acetic acidReflux
3,6-Diiodocarbazole (4) [9]. Carbazole 1, 12.23 g(73 mmol), was dissolved in boiling glacial acetic acid(300 mL), and potassium iodide (15.84 g, 95 mmol)was added. The solution was cooled, ground potassiumiodate (23.42 g, 150 mmol) was added, and the mixturewas refluxed until it acquired a clear straw-colored tint(10 min). The hot solution was decanted from theundissolved potassium iodate and was allowed to cooldown to 45°C. The faintly brown plates were rapidlyfiltered off and recrystallized from alcohol. Yield 5.75 g(18.79 percent), brown solid, mp 202°C [9]. 1H NMRspectrum (400 MHz, CDCl3), δ, ppm: 8.34 s (2H), 8.16br.s (1H), 7.70 d.d (2H, J = 8.53, 1.63 Hz), 7.23 d (2H,J = 8.41 Hz). 13C NMR spectrum (100 MHz, CDCl3),δC, ppm: 138.5, 134.8, 129.4, 124.5, 112.7, 82.5. Massspectrum (MALDI-TOF): m/z 418.551 [M]+. Calculated:M 418.87.
Reference：
[1] Chemistry - An Asian Journal, 2010, vol. 5, # 10, p. 2162 - 2167
[2] Patent: US2009/54649, 2009, A1, . Location in patent: Page/Page column 34-35
[3] Chemistry - A European Journal, 2015, vol. 21, # 48, p. 17379 - 17390
[4] Journal of Organic Chemistry, 2015, vol. 80, # 4, p. 2392 - 2396
[5] European Journal of Organic Chemistry, 2013, # 29, p. 6619 - 6628
[6] Journal of Organic Chemistry, 2016, vol. 81, # 17, p. 7751 - 7759
[7] Patent: WO2012/88316, 2012, A1, . Location in patent: Page/Page column 45-49
[8] Journal of Materials Chemistry, 1999, vol. 9, # 4, p. 893 - 898
[9] Polymer, 2015, vol. 59, p. 57 - 66
[10] Angewandte Chemie, International Edition, 2015, vol. 54, # 19, p. 5677 - 5682[11] Angewandte Chemie, 2015, vol. 127, # 19, p. 5769 - 5774,6
[12] Patent: CN103694992, 2016, B, . Location in patent: Paragraph 0071-0075
[13] Chinese Journal of Chemistry, 2015, vol. 33, # 5, p. 550 - 558
[14] New Journal of Chemistry, 2013, vol. 37, # 10, p. 3252 - 3260
[15] Chinese Journal of Chemistry, 2014, vol. 32, # 4, p. 298 - 306
[16] Russian Journal of Physical Chemistry A, 2016, vol. 90, # 13, p. 2590 - 2599
[17] Polymer, 2012, vol. 53, # 22, p. 4983 - 4992,10
[18] Dyes and Pigments, 2017, vol. 140, p. 79 - 86
[19] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 19, p. 4168 - 4177
[20] Structural Chemistry, 2015, vol. 26, # 4, p. 997 - 1006
[21] Patent: US2012/302675, 2012, A1, . Location in patent: Page/Page column 11-12
[22] Journal of Organic Chemistry, 2015, vol. 80, # 18, p. 9126 - 9131
[23] Bulletin of the Korean Chemical Society, 2016, vol. 37, # 10, p. 1710 - 1716
[24] European Journal of Organic Chemistry, 2016, vol. 2016, # 23, p. 4020 - 4031
[25] Journal of the American Chemical Society, 2011, vol. 133, # 5, p. 1428 - 1437
[26] Journal of Chemistry, 2016, vol. 2016,
[27] Russian Journal of General Chemistry, 2017, vol. 87, # 8, p. 1800 - 1812[28] Zh. Obshch. Khim., 2017, vol. 87, # 8, p. 13
[29] Organic Letters, 2013, vol. 15, # 1, p. 164 - 167
[30] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 4, p. 1096
[31] Chemistry Letters, 2003, vol. 32, # 8, p. 674 - 675
[32] Macromolecules, 2004, vol. 37, # 15, p. 5531 - 5537
[33] European Journal of Organic Chemistry, 2008, # 6, p. 1065 - 1071
[34] Journal of the American Chemical Society, 2009, vol. 131, p. 2244 - 2251
[35] Chemical Communications, 2010, vol. 46, # 7, p. 1088 - 1090
[36] Dalton Transactions, 2011, vol. 40, # 12, p. 2947 - 2953
[37] Reactive and Functional Polymers, 2010, vol. 70, # 7, p. 477 - 481
[38] Journal of Materials Chemistry, 2012, vol. 22, # 13, p. 6374 - 6382
[39] European Journal of Organic Chemistry, 2013, # 34, p. 7785 - 7799
[40] Dyes and Pigments, 2014, vol. 100, # 1, p. 269 - 277
[41] Dyes and Pigments, 2014, vol. 106, p. 1 - 6
[42] Revue Roumaine de Chimie, 2013, vol. 58, # 2-3, p. 113 - 119
[43] Tetrahedron, 2014, vol. 70, # 25, p. 3847 - 3853
[44] Advanced Functional Materials, 2013, vol. 23, # 5, p. 619 - 628
[45] Chinese Chemical Letters, 2016, vol. 27, # 3, p. 441 - 446
[46] Chinese Journal of Chemistry, 2017, vol. 35, # 12, p. 1869 - 1874
[47] Dyes and Pigments, 2015, vol. 113, p. 640 - 648
[48] RSC Advances, 2015, vol. 5, # 74, p. 59960 - 59969
[49] RSC Advances, 2015, vol. 5, # 87, p. 70904 - 70909
[50] Journal of Molecular Structure, 2017, vol. 1127, p. 31 - 42
[51] Patent: KR2015/124473, 2015, A, . Location in patent: Paragraph 0062-0064
[52] Tetrahedron, 2017, vol. 73, # 3, p. 278 - 289
[53] Electrochimica Acta, 2017, vol. 246, p. 1052 - 1064
5
[ 86-74-8 ]
[ 16807-13-9 ]
[ 57103-02-3 ]
Yield
Reaction Conditions
Operation in experiment
70%
Stage #1: With sodium periodate; sulfuric acid; iodine In ethanol at 65℃; for 1 h; Stage #2: With sodium hydroxide In ethanol
To an ethanol solution (500 mL) of carbazole (2.50 g, 15.0 mmol), NaIO4 (0.80 g, 3.75 mmol) and I2 (1.89 g, 7.45 mmol) were added in this order, and then an ethanol solution (100 mL) of H2SO4 (1.60 mL, 30.0 mmol) was added thereto. The reaction solution was heated to reflux for one hour at 65°C. Disappearance of the raw materials was confirmed by TLC (HexH:AcOEt = 4:1), and an ethanol solution (100 mL) of NaOH (1.4 g) was added thereto to neutralize the reaction solution. Ethanol was removed, and then the reaction solution was extracted two times with chloroform and washed two times with water. The organic phase was dried over Na2SO4, and the solvent was removed. The residue was purified by column chromatography (HexH:AcOEt = 4:1), and compound (1) (3.06g, 70percent) was obtained as a white powder. Thus, 3,6-diiodocarbazole (0.47 g, 7.5percent) was obtained as a white powder. 1: 1H NMR (DMSO-d6) 5 11.4 (s, 1H), 8.49 (d, 1H, J = 1.7 Hz), 8.14 (d, 1H, J = 8.0 Hz), 7.62 (dd, 1H, J = 8.4, 1.7 Hz), 7.48 (d, 1H, J = 8.0 Hz), 7.40 (m, 1H), 7.33 (d, 2H, J = 8.4 Hz), 7.16 (m, 1H). 3,6-Diiodocarbazole: 1H NMR (DMSO-d6) δ 11.5 (s, 1H), 8.56 (d, 2H, J = 1.7 Hz), 7.65 (dd, 2H, J = 8.5, 1.7 Hz), 7.34 (d, 2H, J = 8.5 Hz).
70%
Stage #1: With sodium periodate; sulfuric acid; iodine In ethanol at 65℃; for 1 h; Stage #2: With sodium hydroxide In ethanol
To an ethanol solution (500 mL) of carbazole (2.50 g, 15.0 mmol), NaIO4 (0.80 g, 3.75 mmol) and I2 (1.89 g, 7.45 mmol) were sequentially added, and then an ethanol solution (100 mL) of H2SO4 (1.60 mL, 30.0 mmol) was added. The reaction solution was refluxed for one hour at 65° C. The loss of raw materials was confirmed by TLC (HexH:AcOEt=4:1), and an ethanol solution (100 mL) of NaOH (1.4 g) was added thereto to neutralize the system. Ethanol was removed, and then the reaction solution was extracted two times with chloroform. The extract was washed two times with water. The organic phase was dried over Na2SO4, and the solvent was removed. The residue was purified by column chromatography (HexH:AcOEt=4:1), and thus compound 1 (3.06 g, 70percent) was obtained as a white powder. Thus, 3,6-diiodocarbazole (0.47 g, 7.5percent) was obtained as a white powder.1: 1H NMR (DMSO-d6) δ 11.4 (s, 1H), 8.49 (d, 1H, J=1.7 Hz), 8.14 (d, 1H, J=8.0 Hz), 7.62 (dd, 1H, J=8.4, 1.7 Hz), 7.48 (d, 1H, J=8.0 Hz), 7.40 (m, 1H), 7.33 (d, 2H, J=8.4 Hz), 7.16 (m, 1H).3,6-Diiodocarbazole: 1H NMR (DMSO-d6) δ 11.5 (s, 1H), 8.56 (d, 2H, J=1.7 Hz), 7.65 (dd, 2H, J=8.5, 1.7 Hz), 7.34 (d, 2H, J=8.5 Hz).
Reference：
[1] Patent: EP2216338, 2010, A1, . Location in patent: Page/Page column 10
[2] Patent: US2011/34683, 2011, A1, . Location in patent: Page/Page column 9; 10
[3] Journal of Organic Chemistry, 2015, vol. 80, # 4, p. 2392 - 2396
[4] Journal of Organic Chemistry, 2011, vol. 76, # 14, p. 5685 - 5695
[5] Journal of the Chemical Society, 1926, p. 549
[6] Tetrahedron Letters, 2006, vol. 47, # 39, p. 6957 - 6960
[7] Dyes and Pigments, 2017, vol. 137, p. 24 - 35
[8] Journal of Materials Chemistry C, 2017, vol. 5, # 38, p. 9854 - 9864
[9] Dyes and Pigments, 2018, vol. 159, p. 173 - 178
6
[ 1592-95-6 ]
[ 100-44-7 ]
[ 57103-02-3 ]
Reference：
[1] Patent: US2011/309345, 2011, A1,
7
[ 86-74-8 ]
[ 57103-02-3 ]
[ 96853-45-1 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
8
[ 86-74-8 ]
[ 16807-13-9 ]
[ 57103-02-3 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
9
[ 16807-13-9 ]
[ 57103-02-3 ]
[ 96853-45-1 ]
Reference：
[1] Russian Journal of Organic Chemistry, 2003, vol. 39, # 6, p. 875 - 880
10
[ 86-74-8 ]
[ 57103-02-3 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
11
[ 86-74-8 ]
[ 57103-02-3 ]
Reference：
[1] Patent: US2011/309345, 2011, A1,
12
[ 86-74-8 ]
[ 16807-13-9 ]
[ 57103-02-3 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2001, vol. 38, # 1, p. 77 - 87
[2] Russian Journal of Organic Chemistry, 2003, vol. 39, # 6, p. 875 - 880
13
[ 57103-02-3 ]
[ 98-80-6 ]
[ 56525-79-2 ]
Reference：
[1] Journal of the American Chemical Society, 2003, vol. 125, # 5, p. 1140 - 1141
[2] Heterocycles, 2007, vol. 72, p. 133 - 138
[3] Tetrahedron, 2010, vol. 66, # 39, p. 7707 - 7719
A solution of <strong>[57103-02-3]3,6-diiodocarbazole</strong> (5.00 g, 0.012 mol) was placed in a 100 mL round-bottomed flask and 50 mL of acetic anhydride was added. At the same time, 0.1 mL of boron trifluoride etherate was added and the mixture was refluxed for 20 min. Solid, filtration, drying can be obtained after the appearance of white, like flour products 5. 4g; yield 98%
82%
With boron trifluoride diethyl etherate; for 1h;Reflux;
To a mixture of Compound I-Cz (48.60 g, 116 mmol) and acetic anhydride (188.5 mL), was added with boron trifluoride diethyletherate (2.23 mL). Then, the reaction mixture was refluxed for 1 hand cooled to room temperature. During this procedure, a large amount of product I-Cz-Amide was precipitated. After separated by filtration, the crude product was sequently washed with water and alcohol, affording pure I-Cz-Amide (43.61 g) as brown solid in a yield of 82%.
With triethylamine;bis(acetonitrile)(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; In N,N-dimethyl-formamide; at 20 - 80℃; for 7h;
A mixture of 1.0 g (2.39 mmol) of the <strong>[57103-02-3]3,6-diiodocarbazole</strong> obtained as described above and 45 mg (0.12 mmol, 5 mol %) of [Rh(CH3CN)2(cod)]BF4 was added with 20 mL of dimethylformamide (DMF) and 1.99 ml (27 mmol, 6 eq.) of triethylamine (TEA) under a nitrogen atmosphere. Then, the resultant mixture was stirred under a nitrogen atmosphere at room temperature for 30 minutes to obtain a mixed solution. Subsequently, the mixed solution thus obtained was added dropwise with 1.76 ml (18 mmol, 4 eq.) of triethoxysilane [(EtO)3SiH] at room temperature, and stirred under a nitrogen atmosphere at 80 C. for 7 hours. Thereby, a reaction mixture (II) was obtained. Thereafter, the solvent in the reaction mixture (II) thus obtained was removed by distillation with a vacuum pump, and a residue was extracted with ether. After that, a salt thus formed was removed by filtering with celite. The solvent was removed by distillation from the organic phase with an evaporator to obtain a crude product (II). Then, the crude product (II) thus obtained was dissolved in 150 ml of ether, and purified by filtering the resultant through activated carbon (Kiriyama funnel, diameter: 5 cm, thickness: 7 mm). Thereby, a carbazole-silane compound was obtained (a yield of 1.097 g and 89%).The carbazole-silane compound thus obtained was subjected to 13C NMR and 1H NMR measurements. FIG. 66 shows a graph obtained from the 13C NMR measurement, and FIGS. 67 and 68 show graphs obtained from the 1H-NMR measurements. These measurement results are shown below.1H NMR (CDCl3) delta8.46 (d, J=0.8 Hz, 2H), 8.26 (s, 1H), 7.72 (dd, J=7.8 Hz, 0.8 Hz, 2H), 7.43 (dd, J=7.7, 0.8 Hz, 2H), 3.93 (q, J=7.3 Hz, 12H), 1.29 (t, J=7.3 Hz, 18H);13C NMR (CDCl3) delta140.85, 131.83, 127.39, 122.70, 119.78, 110.49, 58.72, 18.29.Based on the NMR measurement results, it was confirmed that the carbazole-silane compound obtained in Example 20 was a carbazole-disilane compound expressed by the following general formula (95).
With potassium hydroxide; In acetone; for 0.25h;Reflux;
To a solution of 1 (1.5 g, 3.58 mmol) and KOH (0.92 g,16.4 mmol) in acetone (20 mL) was added slowly a solution of p-toluenesulfonyl chloride (3.127 g, 16.4 mmol) in acetone (2 mL). The reaction mixture was reflux for 15 min, then poured into water and extracted with CH2Cl2. The combined organic phase was washed with water, brine, dried over anhydrous MgSO4, filtered, and concentrated. Purification by recrystallization (CH2Cl2/petroleum ether) gave 2 as a yellow solid (1.44 g, 70%). 1H NMR (600 MHz,CDCl3): delta 8.17 (d, J 1.2 Hz, 2H), 8.07 (d, J 9.0 Hz, 2H), 7.78 (dd,J 9.0,1.8 Hz, 2H), 7.65 (d, J 8.4 Hz, 2H), 7.13 (d, J 7.8 Hz, 2H), 2.29 (s, 3H).
With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 20℃; for 2h;Cooling with ice;
2I-CZ (4.22 g, 10.02 mmol), p-toluenesulfonyl chloride (TOSCl) (2.23 g, 11.42 mmol), N,N-dimethylformamide (DMF) 40 mL,Sodium hydride (0.93 g, 20.05 mmol) was slowly added under ice-cooling, and allowed to react at room temperature for 2 h. After completion of the reaction, the reactant was poured into water, and the precipitated solid was suction filtered and dried to give a product. The yield was 90%.
To this solution, di-/er/-butyl dicarbonate (6.2 g, 14.4 mmol) was first added, and then 4-dimethylaminopyridine (2 g, 14.4 mmol) was carefully added in small increments (gas evolved). After stirring for 4 hours at room temperature, the precipitate was filtered, the reaction mixture was concentrated to half volume, and the precipitate was filtered again. The same procedure was repeated once more and the precipitates were combined and washed with methanol to give 4 g of DF-I- 25.Yield:90%. NMR (300 MHz, CDC13, delta): delta 8.13 (2.0H, d, J = 1.5 Hz), 7.99 (2.0H, d, J = 8. = 8.8, 1.5 Hz), 1.74 (9.0H, s).
35%
With dmap; In acetone; for 3h;
Into a carbazole (30g, 174 mmol) and 500 mL of acetic acid 1L 2-neck flask (2-neck flask), the back was completely dissolved in about 100 , then cooled. Put KI (39g, 235 mmol), the KIO3 (57g, 266mmol) was stirred slowly . The reaction proceeds for about 15 min, the precipitate was separated, sufficiently washed with distilled water, the separated precipitate. re-precipitated several times to separate the precipitate under a MC / MeOH, after it was separated and dried. Thus obtained was dissolved in 500mL of acetone results, part undissolved after removing, di-tert-butyl dicarbonate (50mL, 217 mmol) into a completely dissolved. Insert after the 4-methylaminopyridine (22g, 180 mmol) was stirred for 3 hours. Formed bag Separating the precipitate of the color, which was performed several times to re-separate the precipitate formed while stirring again, the separated process solution. The separated precipitate was washed with methanol to give the first intermediate compound 32g of (I) (yield: 35%).
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 24h;
To a solution of 3,6 -diiodocarbazole (10.0 g, 23.87 mmol) and 11 -bromo-1- undecanol (7.0 g, 27.87 mmol) in DMF (100.0 ml) was added K 2CO3 (32.0 g, <n="37"/>231.33 mmol). The reaction was carried out at room temperature for 24 h. Water (300 ml) was added. The precipitate was filtered. The crude product was purified by silica gel column using Hexane/ethyl acetate (7 : 3) as solvent. 12.4 g (87.9 %) of pure product as white solid was obtained. 1H-NMR (CDC13, TMS, 500 MHZ): delta = 8.32 (d, 2 Harom, J = 1 -5 Hz), 7.71(dd, 2 Harom, Jl = 1.5 Hz, J2 = 8.5 Hz), 7.16 (dd, 2 H arom, Jl = 1.5 Hz, J2 = 8.5 Hz), 4.21 (t, 2 H, NCH 2), 3.64 (m, 2 H, OCH 2), 3.41 (t, 1 H, OH), 1.81 (m, 4 H, 2 x CH2), 1.54 (m, 4 H, 2 x CH 2), 1.30 (m, 10 H, 5 x CH2) ppm.
87.9%
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 24h;
To a solution of <strong>[57103-02-3]3,6-diiodocarbazole</strong> (10.0 g, 23.87 mmol) and 11-bromo-l-undecanol (7.0 g, 27.87 mmol) in DMF (100.0 ml) was added K2CO3 (32.0 g, 231.33 mmol). The reaction was carried out at room temperature for 24 h. Water (300 ml) was added. The precipitate was filtered. The crude product was purified by silica gel column using Hexane/ethyl acetate (7 : 3) as solvent. 12.4 g (87.9 %) of pure product as white solid was obtained. 1H-NMR (CDCI3, TMS, 500 MHZ): delta = 8.32 (d, 2 Harom, J = 1.5 Hz), 7.71 (dd, 2 HarOm, Jl = 1.5 Hz, J2 = 8.5 Hz), 7.16 (dd, 2 Harom, Jl = 1.5 Hz, J2 = 8.5 Hz), 4.21 (t, 2 H, NCH2), 3.64 (m, 2 H, OCH2), 3.41 (t, 1 H, OH), 1.81 (m, 4 H, 2 x CH2), 1.54 (m, 4 H, 2 x CH2), 1.30 (m, 10 H, 5 x CH2) ppm.
With potassium carbonate; In hexane; water; ethyl acetate; N,N-dimethyl-formamide;
Step 1: 11-(3,6-Diiodo-9H-carbazol-9-yl)undecan-1-ol To a solution of <strong>[57103-02-3]3,6-diiodocarbazole</strong> (10.0 g, 23.87 mmol) and 11-bromo-1-undecanol (7.0 g, 27.87 mmol) in DMF (100.0 ml) was added K2CO3 (32.0 g, 231.33 mmol). The reaction was carried out at room temperature for 24 h. Water (300 ml) was added. The precipitate was filtered. The crude product was purified by silica gel column using Hexane/ethyl acetate (7:3) as solvent. 12.4 g (87.9%) of pure product as white solid was obtained. 1H-NMR (CDCl3, TMS, 500 MHZ): delta=8.32 (d, 2Harom, J=1.5 Hz), 7.71 (dd, 2Harom, J1=1.5 Hz, J2=8.5 Hz), 7.16 (dd, 2Harom, J1=1.5 Hz, J2=8.5 Hz), 4.21 (t, 2H, NCH2), 3.64 (m, 2H, OCH2), 3.41 (t, 1H, OH), 1.81 (m, 4H, 2*CH2), 1.54 (m, 4H, 2*CH2), 1.30 (m, 10H, 5*CH2) ppm.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 90℃; for 24h;Inert atmosphere;
Compound 3(0.89 g, 5.2 mmol) and compound 4 (1.09 g,2.6 mmol) were dissolved in 25 mL toluene in a roundbottom flask under nitrogen. A solution of potassium carbonate (2 M, 6.5 mL) was added to the reaction mixture. Tetrakis(triphenylphosphine)palladium(0)(0.12 g, 0.10 mmol) was added. The reaction mixture was reflux for 24 h under nitrogen. After cooling toroom temperature, the reaction mixture was evaporated to remove solvent and extracted with chloroform and then washed with water. The organic layer was evaporated using a rotary evaporator, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent. White powdery product was obtained (0.67 g, 30.7%). 1H NMR (CDCl3,600 MHz): delta (ppm) = 8.30 (s, 1H), 8.22 (s, 2H), 8.03(d, 2H, J = 8.53 Hz), 7.94 (d, 2H, J = 8.12 Hz), 7.89(dd, 2H, J = 7.36, 1.44 Hz), 7.62 (d, 4H, J = 1.10 Hz),7.54-7.60 (m, 4H), 7.51 (ddd, 2H, J = 7.98, 6.88,1.10 Hz), 7.44 (ddd, 2H, J = 8.32, 6.95, 1.24 Hz). 13CNMR (CDCl3, 100 MHz): delta (ppm) = 140.93, 139.26,133.90, 132.35, 132.18, 128.41, 128.24, 127.36, 127.26,126.34, 125.93, 125.67, 125.42, 123.49, 121.85, 110.39.MALDI-TOF MS (m/z): calcd. for C32H21N 419.17,found 418.905.
9-benzyl-3-bromocarbazole 24 g of 3-bromocarbazole was dissolved in 100 ml of tetrahydrofuran. To this was added 14 g of potassium carbonate followed by 14 g of benzylchloride and allowed the reaction to stir at room temperature overnight. The reaction mixture was poured into water and the precipitated white solid was filtered, washed with methanol and dried under vacuum to obtain 30 g 9-benzyl-3-bromocarbazole (89%).
With sodium t-butanolate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In toluene; at 80℃; for 4h;Inert atmosphere;
Next, the obtained intermediate B was used in accordance with the following method to obtain the intermediate C. That is, first, a two-necked reactor was charged with, in a nitrogen stream, the intermediate B 15.0 g (35.80 mmol) which was obtained above and p-toluenethiol 9.34 g (75.18 mmol), then these were made to dissolve in toluene 350 ml. Next, to this solution, sodium tert-butoxide 17.20 g (179.0 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium (II) dichloride dichloromethane adduct 0.73 g (0.895 mmol) were added and the total volume was made to react at 80 C. for 4 hours. After that, the reaction solution was returned to room temperature, distilled water 1000 ml and saturated sodium chloride solution 500 ml were added, and the result was extracted by ethyl acetate 500 ml. The organic layer was made to dry over anhydrous sodium sulfate, was concentrated by a rotary evaporator, then was purified by silica gel column chromatography (n-hexane: tetrahydrofuran=3:1 (volume ratio)) to thereby obtain the intermediate C in 9.14 g for a yield of 62%. The structure of the obtained intermediate C was identified by 1H-NMR.1H-NMR (500 MHz, CDCl3, TMS, deltappm): 2.29 (s, 6H) 7.05 (d, 4H, J=8.0 Hz), 7.15 (d, 4H, J=8.0 Hz), 7.37 (d, 2H, J=8.5 Hz), 7.51 (dd, 2H, J=8.5, 1.5 Hz), 8.12 (d, 2H, J=1.5 Hz), 8.18 (s, 1H).
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
