* 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.
Reference：
[1] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 872,873[2] Doklady Chemistry, 112-117 <1957> 133, 134,
2
[ 7790-94-5 ]
[ 108-86-1 ]
[ 7664-93-9 ]
[ 138-36-3 ]
[ 2050-48-8 ]
[ 98-58-8 ]
Reference：
[1] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 872,873[2] Doklady Chemistry, 112-117 <1957> 133, 134,
3
[ 108-86-1 ]
[ 98-58-8 ]
[ 2050-48-8 ]
Yield
Reaction Conditions
Operation in experiment
88%
With iron(III) chloride In dichloromethane at 40℃; for 6 h;
4-Bromobenzenesulfonyl chloride (5.00 g, 19.69 mmol) and bromobenzene (4.61 g, 29.54 mmol) were added to a 250 mL three-necked flask.Dissolve in 40 mL of dichloromethane and add ferric chloride (6.34 g,After 39.39 mmol), the reaction solution was heated to 40 ° C and stirred for 6 h.The reaction solution was cooled to room temperature, and 30 mL of dichloromethane was slowly added thereto.50 mL of 1 M dilute hydrochloric acid and stirring for 10 min, the mixed solution was poured into a separatory funnel, the organic layer solution was taken, and the aqueous layer was extracted three times with dichloromethane.The organic layers were combined, dried over anhydrous sodium sulfate and filtered.The resulting filtrate was spin-dried using a rotary evaporator.The crude product was purified by silica gel column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 4:5. The product was dried in vacuo to give a white powder.6.48 g, yield 88percent.
Reference：
[1] Patent: CN108084150, 2018, A, . Location in patent: Paragraph 0086; 0087; 0088; 0089
[2] Recueil des Travaux Chimiques des Pays-Bas, 1910, vol. 29, p. 324
[3] Recueil des Travaux Chimiques des Pays-Bas, 1911, vol. 30, p. 139
[4] Recueil des Travaux Chimiques des Pays-Bas, 1914, vol. 33, p. 130,152[5] Chem. Zentralbl., 1914, vol. 85, # I, p. 2166
4
[ 3393-78-0 ]
[ 2050-48-8 ]
Yield
Reaction Conditions
Operation in experiment
84.66%
for 24 h; Reflux
To a solution of 30mL H2O2 (30percent, g/g) and 30mL of HOAc was added 3c (3.44g, 10mmol) in fractions. After heated under reflux for 24h, the resulting mixture was cooled to room temperature and then poured into water. The white precipitate was filtered and dried. The crude product was recrystallized from ethanol to produce 3b as a white solid. Yield: 84.66percent. M.p.:173–174°C. 1H NMR (300MHz, CDCl3): δ(ppm) 7.80–7.77 (d, J=8.7Hz, 4H), 7.67–7.64 (d, J=8.7Hz, 4H) [36].
51%
at 100℃; for 10 h;
Well dried 250 mL three-necked round bottom flask charged with bis (4-bromophenyl) sulfane (9 g, 26.2 mmol), 30percent hydrogenperoxide 50 mL and acetic acid 100 mL was stirred at 100°C for 10 hours. After completion of the reaction, it was extracted three times using methylenechloride (MC). The extracted organic layer was dried to remove water using MgSO4 and the solvent was removed using a rotary evaporator, separated by column chromatography using MC to obtain compound 5 g (yield = 51percent).
Reference：
[1] Macromolecules, 2014, vol. 47, # 9, p. 2907 - 2914
[2] Dyes and Pigments, 2014, vol. 111, p. 135 - 144
[3] Chemistry of Materials, 2013, vol. 25, # 13, p. 2630 - 2637
[4] Patent: KR2016/73914, 2016, A, . Location in patent: Paragraph 0189-0190; 0195-0197
[5] Journal of the American Chemical Society, 1946, vol. 68, p. 973,974, 976, 2671[6] Journal of the American Chemical Society, 1947, vol. 69, p. 644,2310
[7] Recueil des Travaux Chimiques des Pays-Bas, 1911, vol. 30, p. 417
[8] Recueil des Travaux Chimiques des Pays-Bas, 1935, vol. 54, p. 711,715
[9] Journal of Polymer Science, Part A: Polymer Chemistry, 2016, vol. 54, # 21, p. 3454 - 3461
[10] Patent: CN105524070, 2016, A, . Location in patent: Paragraph 0090; 0091; 0092; 0093; 0166-0169
5
[ 34176-08-4 ]
[ 2050-48-8 ]
Yield
Reaction Conditions
Operation in experiment
91%
With copper diacetate In acetonitrile at 60℃; for 3 h;
General procedure: A mixture of the sodium arylsulfinate (1 mmol), Cu(OAc)2 (0.5 mmol)and CH3CN (1 mL) was stirred at 60 °C in air for 3 h. After this, themixture was cooled to room temperature and filtered through a filterpaper. The organic phases were evaporated under reduced pressure andthe residue was subjected to flash column chromatography (silica gel,ethyl acetate/petroleum ether = 1/10) to obtain the desired product.All products are known compounds and were characterised by 1HNMR, 13C NMR and HRMS.
Reference：
[1] Journal of Chemical Research, 2014, vol. 38, # 5, p. 265 - 268
6
[ 108-86-1 ]
[ 2050-48-8 ]
Reference：
[1] Chemical Communications, 2014, vol. 50, # 95, p. 15037 - 15040
[2] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 872,873[3] Doklady Chemistry, 112-117 <1957> 133, 134,
[4] Patent: US2860168, 1957, ,
[5] Justus Liebigs Annalen der Chemie, 1879, vol. 197, p. 257
[6] Chemische Berichte, 1875, vol. 8, p. 595
[7] Bulletin de la Societe Chimique de France, 1923, vol. <4> 33, p. 183
[8] Chemische Berichte, 1878, vol. 11, p. 2066
[9] Journal of the Chemical Society, 1871, vol. 24, p. 174[10] Chemische Berichte, 1882, vol. 15, p. 205
7
[ 1774-37-4 ]
[ 2050-48-8 ]
Reference：
[1] Russian Journal of Organic Chemistry, 1995, vol. 31, # 11, p. 1520 - 1525[2] Zhurnal Organicheskoi Khimii, 1995, vol. 31, # 11, p. 1692 - 1697
[3] Canadian Journal of Chemistry, 1987, vol. 65, p. 2421 - 2424
[4] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1981, vol. 20, # 5, p. 505 - 506
[5] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1986, vol. 25, # 7, p. 678 - 680
[6] Journal of the Indian Chemical Society, 1992, vol. 69, # 12, p. 819 - 821
[7] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1989, vol. 28, # 3, p. 250 - 252
[8] Recueil des Travaux Chimiques des Pays-Bas, 1910, vol. 29, p. 324
[9] Magnetic Resonance in Chemistry, 1989, vol. 27, # 4, p. 360 - 367
[10] Tetrahedron, 2001, vol. 57, # 7, p. 1369 - 1374
[11] Journal of Chemical Research, Miniprint, 2000, # 10, p. 1118 - 1133
[12] Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, 2005, vol. 44, # 1, p. 71 - 75
[13] Journal of the Indian Chemical Society, 2007, vol. 84, # 7, p. 679 - 682
8
[ 3393-78-0 ]
[ 1774-37-4 ]
[ 2050-48-8 ]
Reference：
[1] Journal of Materials Chemistry C, 2016, vol. 4, # 19, p. 4288 - 4295
9
[ 589-87-7 ]
[ 2050-48-8 ]
Reference：
[1] Dyes and Pigments, 2014, vol. 111, p. 135 - 144
[2] Patent: KR2016/73914, 2016, A,
10
[ 106-53-6 ]
[ 2050-48-8 ]
Reference：
[1] Dyes and Pigments, 2014, vol. 111, p. 135 - 144
11
[ 108-86-1 ]
[ 498-83-9 ]
[ 2050-48-8 ]
[ 141223-29-2 ]
[ 141223-30-5 ]
Reference：
[1] Journal of Organic Chemistry, 1992, vol. 57, # 13, p. 3738 - 3740
12
[ 139-66-2 ]
[ 2050-48-8 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1911, vol. 30, p. 417
[2] Chemistry of Materials, 2013, vol. 25, # 13, p. 2630 - 2637
13
[ 108-86-1 ]
[ 2050-48-8 ]
[ 76619-21-1 ]
Reference：
[1] Liebigs Annalen der Chemie, 1982, # 2, p. 282 - 297
14
[ 108-86-1 ]
[ 138-36-3 ]
[ 2050-48-8 ]
Reference：
[1] Chemische Berichte, 1878, vol. 11, p. 2066
[2] Chemische Berichte, 1875, vol. 8, p. 595
[3] Journal of the Chemical Society, 1871, vol. 24, p. 174[4] Chemische Berichte, 1882, vol. 15, p. 205
15
[ 80-08-0 ]
[ 2050-48-8 ]
Reference：
[1] Bulletin des Societes Chimiques Belges, 1987, vol. 96, # 1, p. 41 - 50
16
[ 7790-94-5 ]
[ 108-86-1 ]
[ 138-36-3 ]
[ 2050-48-8 ]
Reference：
[1] Chemische Berichte, 1878, vol. 11, p. 2066
[2] Chemische Berichte, 1875, vol. 8, p. 595
[3] Journal of the Chemical Society, 1871, vol. 24, p. 174[4] Chemische Berichte, 1882, vol. 15, p. 205
17
[ 108-86-1 ]
[ 7664-93-9 ]
[ 138-36-3 ]
[ 2050-48-8 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1879, vol. 197, p. 257
18
[ 108-86-1 ]
[ 7446-11-9 ]
[ 138-36-3 ]
[ 2050-48-8 ]
Reference：
[1] Chemische Berichte, 1875, vol. 8, p. 595
19
[ 7790-94-5 ]
[ 108-86-1 ]
[ 138-36-3 ]
[ 2050-48-8 ]
[ 98-58-8 ]
Reference：
[1] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 872,873[2] Doklady Chemistry, 112-117 <1957> 133, 134,
20
[ 7790-94-5 ]
[ 108-86-1 ]
[ 7664-93-9 ]
[ 138-36-3 ]
[ 2050-48-8 ]
[ 98-58-8 ]
Reference：
[1] Doklady Akademii Nauk SSSR, 1957, vol. 112, p. 872,873[2] Doklady Chemistry, 112-117 <1957> 133, 134,
21
[ 2050-48-8 ]
[ 7545-50-8 ]
Reference：
[1] Chemical Communications, 2014, vol. 50, # 95, p. 15037 - 15040
With oxygen; epi-Cercosporin; In methanol; at 25℃; for 24h;Irradiation;
In a 10 mL reaction tube, cercosporin (0.005 mmol) and 4,4'-dibromophenyl sulfide (0.5 mmol) were sequentially added.2mL of methanol, then oxygen protection, 15W white light irradiation, room temperature 25 C reaction for 24h.Rapid object separated by thin layer silica gel plates 300-500 The reaction solution was evaporated to dryness using a rotary evaporator the solvent used is acetic acid eluent ethyl acetate / petroleum ether (v: v = 1: 5),4,4'-Dibromophenyl sulfone was obtained in a yield of 86%.
84.66%
With dihydrogen peroxide; acetic acid; for 24h;Reflux;
To a solution of 30mL H2O2 (30%, g/g) and 30mL of HOAc was added 3c (3.44g, 10mmol) in fractions. After heated under reflux for 24h, the resulting mixture was cooled to room temperature and then poured into water. The white precipitate was filtered and dried. The crude product was recrystallized from ethanol to produce 3b as a white solid. Yield: 84.66%. M.p.:173-174C. 1H NMR (300MHz, CDCl3): delta(ppm) 7.80-7.77 (d, J=8.7Hz, 4H), 7.67-7.64 (d, J=8.7Hz, 4H) [36].
51%
With dihydrogen peroxide; acetic acid; at 100℃; for 10h;
Well dried 250 mL three-necked round bottom flask charged with bis (4-bromophenyl) sulfane (9 g, 26.2 mmol), 30% hydrogenperoxide 50 mL and acetic acid 100 mL was stirred at 100C for 10 hours. After completion of the reaction, it was extracted three times using methylenechloride (MC). The extracted organic layer was dried to remove water using MgSO4 and the solvent was removed using a rotary evaporator, separated by column chromatography using MC to obtain compound 5 g (yield = 51%).
With dihydrogen peroxide; acetic acid; for 8h;Inert atmosphere; Reflux;
In N2Gas purification system, and the acetic acid was stirred into compound G.Added in excess 30% hydrogen peroxide.The mixture was refluxed for 8 hours at the temperature 110 reaction was complete.The mixture was cooled to room temperature, water was added and the precipitate.The mixture was stirred for about 30 minutes, the precipitate is filtered off.The resultant was washed with water, to obtain a compound H.
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 40℃; for 10h;
In a three-necked flaskDiphenylthiophenol (4g, 0.021mol) was added to it.Connect the three links and add balloons,Br2 (9.95 g, 0.063 mol) was poured in a syringe and stirred at room temperature for 2 h to give a yellow solid.The above yellow solid was dissolved in DCM, and stirred at 2.5 eq.After cooling to room temperature, a white precipitate appeared after stirring with K2CO3.The filtrate was filtered and evaporated to dryness to give a white solid.
With dihydrogen peroxide; acetic acid; for 10h;
Diphenylsulfane (4 g, 0.021 mol) and Br2 (9.95 g, 0.063 mol) wereadded into a flask to stir at room temperature for 6h. After that, 300 mLmixed solution of H2O2:CH3COOH 1:1 (v: v) was added to react for 10h, and was further purified by silica gel column chromatography to givewhite solid, with yield of 73%. 1H NMR (400 MHz, Chloroform-d) 7.81-7.76 (m, 4H), 7.68-7.63 (m, 4H). 13C NMR (101 MHz, Chloroformd) 141.63, 133.18, 129.28, 127.66.
With iron(III) chloride; In dichloromethane; at 40℃; for 6h;
4-Bromobenzenesulfonyl chloride (5.00 g, 19.69 mmol) and bromobenzene (4.61 g, 29.54 mmol) were added to a 250 mL three-necked flask.Dissolve in 40 mL of dichloromethane and add ferric chloride (6.34 g,After 39.39 mmol), the reaction solution was heated to 40 C and stirred for 6 h.The reaction solution was cooled to room temperature, and 30 mL of dichloromethane was slowly added thereto.50 mL of 1 M dilute hydrochloric acid and stirring for 10 min, the mixed solution was poured into a separatory funnel, the organic layer solution was taken, and the aqueous layer was extracted three times with dichloromethane.The organic layers were combined, dried over anhydrous sodium sulfate and filtered.The resulting filtrate was spin-dried using a rotary evaporator.The crude product was purified by silica gel column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 4:5. The product was dried in vacuo to give a white powder.6.48 g, yield 88%.
Typical examples of the compound represented by the formula (5) include 4,4'-difluorobenzophenone, ... 4,4'-dichlorodiphenylsulfone, 4,4'-dichloro-3,3'-disulfodiphenylsulfone, dipotassium salt of 4,4'-dichloro-3,3'-disulfodiphenylsulfone, disodium salt of 4,4'-dichloro-3,3'-disulfodiphenylsulfone, 4,4'-dibromodiphenylsulfone, 4,4'-dinitrodiphenylsulfone, 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile,
With copper diacetate; In acetonitrile; at 60℃; for 3h;
General procedure: A mixture of the sodium arylsulfinate (1 mmol), Cu(OAc)2 (0.5 mmol)and CH3CN (1 mL) was stirred at 60 C in air for 3 h. After this, themixture was cooled to room temperature and filtered through a filterpaper. The organic phases were evaporated under reduced pressure andthe residue was subjected to flash column chromatography (silica gel,ethyl acetate/petroleum ether = 1/10) to obtain the desired product.All products are known compounds and were characterised by 1HNMR, 13C NMR and HRMS.
To a solution of 3b (0.376g, 1.0mmol), 18-crown-6 (0.027g, 0.1mmol) and 3,6-di(tert-butyl)carbazole (0.68g, 2.4mmol) in DMPU (5mL) was added K2CO3 (0.55g, 4.0mmol). The reaction mixture was then purged with nitrogen for ten minutes before adding CuI (0.020g, 0.1mmol). The following procedure was similar to that used for 1a. Yield: 58.21%. M.p.:367-370C. 1H NMR (300MHz, CDCl3): delta (ppm) 8.26-8.23 (d, J=8.4Hz, 4H), 8.13 (s, 4H), 7.83-7.80 (d, J=8.4Hz, 2H), 7.50-7.43 (m, 8H), 1.46 (s, 36H). 13C NMR (75MHz, CDCl3): delta (ppm) 143.7, 142.8, 138.4, 137.9, 129.2, 126.2, 123.7, 123.6, 116.1, 108.8, 34.4, 31.6. MS (MALDI-TOF) [m/z]: calcd for C52H56N2O2S, 772.41; found, 772.5745. Anal. Calcd. for C52H56N2O2S (%): C, 80.79; H, 7.30; N 3.62; S, 4.15.found:C, 80.62; H, 7.38; N 3.67; S, 4.17.
10-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-phenoxazine[ No CAS ]
C48H32N2O4S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; at 80℃; for 24h;Inert atmosphere;
P 20 synthetic: under the protection of the argon, will be 4, the 4 [...] - two bromine benzoin sulphone (10mmol, 3 . 4g), M 17 (25mmol, 9 . 63g), potassium carbonate (2.0MinH 2 O, 10 ml, 20mmol), Pd (PPh 3) 4 (0.4mmol, 461mg), THF (50 ml), toluene (100 ml) in 250 ml three-mouth bottle, 80 C reaction under 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the white solid 6.01g, yield 82%.
9,9-dimethyl-10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydroacridine[ No CAS ]
C54H44N2O2S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; at 80℃; for 24h;Inert atmosphere;
P 6 synthetic: under the protection of the argon, will be 4, the 4 [...] - two bromine benzoin sulphone (10mmol, 3 . 4g), M 14 (25mmol, 10 . 28g), potassium carbonate (2.0MinH 2 O, 10 ml, 20mmol), Pd (PPh 3) 4 (0.4mmol, 461mg), THF (50 ml), toluene (100 ml) in 250 ml three-mouth bottle, 80 C reaction under 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the white solid 6.36g, yield 81%.
With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; Reflux;
M2 synthesis: under the protection of argon, a 4, 4 '- dibromo-diphenyl sulfone (lOmmol, 3 · 76g), Mu: (20mmol,3. 02g) into 250ml three-necked reaction flask, 100ml toluene to dissolve them. After dissolution, followed by adding tSodium butyl alcohol (4. 8g, 50mmol), three-tert-butyl phosphine (0. 5ml, lM / L) and palladium acetate (112mg, 0. 5mmol), dark green system. After feeding is finished, heated to 110 c, reflux, the reaction 24h. After completion of the reaction, washed with water and a yellow solid was obtained 4.34 g of the separation column, a yield of 84% methylene chloride and extracted
10,10'-(sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 12h;Inert atmosphere;
In N2in the gas purification system, the use of a compound "d" (0.3mol), 4-bromobenzyl sulfone (0.15mol), Pd (OAc)2(6.11mmol), P(t-Bu)3(50 wt %, 15 . 28mmol) sodium and tertiary butyl alcohol (0.61mol) is added to the toluene solvent and stirring. In the solution 120 C and the temperature of the refluxing under stirring 12 hours. After the completion of reaction, the solution is cooled to the room temperature and water and ethyl acetate extraction. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the solvent. The material through the use of hexane and ethyl acetate to carry out wet refining column chromatography, thereby obtaining compound 20. (Yield: 80%)
With potassium carbonate; palladium; In tetrahydrofuran; water; at 80℃;Inert atmosphere;
In N2in the gas purification system, the 4-phenyl bromine sulphone soluble in toluene solvent, and by adding phenyl boronic acid (0.9 equiv). The K2CO3(4 equivalent) dissolved in distilled water in and added to the solution. By adding tetrahydrofuran solvent, and by adding palladium (0.05 equiv). The mixture at 80 C and the temperature of the refluxing under stirring. After the reaction is finished, the ethyl ester of acetic acid and distilled water to the mixture to extraction. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of hexane and ethyl acetate to carry out wet refining column chromatography, thereby obtaining solid compound "h". (Yield: 75%)
9,9-dimethyl-10-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9.10-dihydroacridine[ No CAS ]
C54H44N2O2S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
With potassium carbonate; palladium; In tetrahydrofuran; water; at 80℃;Inert atmosphere;
In N2in the gas purification system, the 4-bromobenzyl sulfone in toluene solvent-soluble, "e" and the compound is added (2.4 equivalent). The K2CO3(8.8 equivalent) dissolved in distilled water in and added to the solution. By adding tetrahydrofuran solvent, and by adding palladium (0.1 equivalent). The mixture at 80 C and the temperature of the refluxing under stirring. After the completion of reaction, using aqueous sodium hydroxide solution and toluene extraction mixture. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. Through the resulting column chromatography using hexane to carry out wet refining crystallization, so as to obtain compound 13. (Yield: 78%)
9-(4-((4-bromophenyl)sulfonyl)phenyl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 20h;Inert atmosphere;
9H-carbazole (100 g, 598 mmol) was added in a nitrogen atmosphereAfter dissolving in 1,900 mL of toluene,Here 4,4'-sulfonylbis(Bromobenzene)(270 g, 718 mmol), Tris (diphenylideneacetone) dipalladium (0) (5.48 g, 5.98 mmol),Tris-tert-butylphosphine (6.05 g, 29.9 mmol) And sodium tert-butoxide (69.0 g, 718 mmol) And the mixture was refluxed by heating at 100 DEG C for 20 hours.After completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane. Then, water was removed with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-5 (243 g, 88%).
75%
With potassium dihydrogenphosphate; copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane; In 1,4-dioxane; at 110℃;Inert atmosphere;
4,4'-sulfonyldi(bromobenzene) (20 g, 53.18 mmol) under nitrogen1,4-dioxane (400 ml), after dissolution, adding cuprous iodide (10 g) and potassium phosphate (20 g),Carbazole (9.8 g, 58.5 mmol) and trans-1,2-cyclohexanediamine (6.7 g, 58.5 mmol).Stir at 110 C, after completion of the reaction, extract with anhydrous acetone (300 ml) and ethyl acetate (400 ml).Compound 1-5 (18.4 g 75%) was obtained.
75%
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine; In 1,4-dioxane; at 110℃;Inert atmosphere;
Under nitrogen conditions, <strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (20 g, 53.18 mmol),1,4-dioxane (400ml), after dissolution, Add cuprous iodide (10g) and potassium phosphate (20g), Carbazole (9.8 g, 58.5 mmol) and trans-1,2-cyclohexanediamine (6.7 g, 58.5 mmol). Stir at 110 C, after the reaction is over, extract with anhydrous acetone (300 ml) and ethyl acetate (400 ml). Compound 1-5 (18.4 g 75%) was obtained.
60%
With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine; In 1,4-dioxane; at 110℃; for 24h;Inert atmosphere;
In N2in the gas purification system, the carbazole is dissolved in 1,4-dioxane solvent, and by adding CuI and K3PO4. Add another 4-bromobenzyl sulfone (1.1 equivalent) and trans -1,2-diamino cyclohexane. In the solution 110 C and the temperature of the refluxing under stirring 24 hours. After the completion of reaction, to the room temperature and cooling the solution and distilled water extraction by ethyl acetate. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of hexane and ethyl acetate to carry out wet refining column chromatography, thereby obtaining compound "i". (Yield: 60%)
With potassium phosphate; copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux;
In N2Gas purification system, Compound A (1 eq.) Was dissolved in 1,4-dioxane was added CuI and K3PO4.Compound H (1.1 equiv) and trans-1,2-diaminocyclohexane added to the flask containing compound A.At temperature 110 the mixture was stirred at reflux for 24 hours.After the reaction was complete, the mixture was cooled to room temperature, water and ethyl acetate.The resultant ethyl acetate and hexane solvent through the column to obtain compound I.
9-(4'-((4-bromophenyl)sulfonyl)-[1,1'-biphenyl]-4-yl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With potassium carbonate; palladium; In tetrahydrofuran; water; at 80℃;Inert atmosphere;
In N2in the gas purification system, the 4-bromobenzyl sulfone soluble in toluene solvent, and "h" compound is added (0.9 equiv). The K2CO3(4 equivalent) dissolved in distilled water in and added to the solution. By adding tetrahydrofuran solvent, and by adding palladium (0.05 equiv). The mixture at 80 C and the temperature of the refluxing under stirring. After the reaction is finished, the ethyl ester of acetic acid and distilled water to the mixture to extraction. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of hexane and ethyl acetate to carry out wet refining column chromatography, thereby obtaining solid compound "j". (Yield: 60%)
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; at 80℃;Inert atmosphere;
<strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (10g, 26.6mmol),4-(Diphenylamino)phenylboronic acid (8.5 g, 29.26 mmol), Potassium carbonate (K2CO3) ( 16.2 g, 117.04 mmol), tetrakistriphenylphosphine palladium (0.1 g),Intermediate 5-1 (10.8 g, 75%) was prepared using the same experimental procedure as Compound 1. Compound 1-5 (15 g, 32.44 mmol), toluene (350 ml), under nitrogenCompound 1-4 (15.94 g, 38.93 mmol) was added.Calcium carbonate (K2CO3) (19.7 g, 142.74 mmol), adding deionized water to the reaction mixture,Tetrahydrofuran (200 ml), tetrakistriphenylphosphine palladium (0.1 g) was added, and the mixture was stirred, and the reaction was refluxed at 80 C.After extraction, it was recrystallized from dichloromethane / n-hexane to give Compound 1 (13.5 g, 63%).
55%
With potassium carbonate; palladium; In tetrahydrofuran; water; at 80℃;Inert atmosphere;
In N2in the gas purification system, the 4-bromobenzyl sulfone soluble in toluene solvent, and by adding 4 - (diphenyl amino) phenyl boronic acid (1.1 equivalent). The K2CO3 (4.4 equiv) dissolved in distilled water in and added to the mixed solution. By adding tetrahydrofuran solvent, and by adding palladium (0.05 equiv). The mixture at 80 C and the temperature of the refluxing under stirring. After the reaction is finished, by ethyl acetate extraction mixture. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of methylene chloride and hexane to carry out wet refining column chromatography, thereby obtaining compound "k". (Yield: 55%)
With potassium carbonate; palladium; In tetrahydrofuran; water; toluene;Inert atmosphere; Reflux;
In N2Gas purification system, the compound H is dissolved in toluene, added compound K (1.1 eq).Will be dissolved in deionized water K2CO3(4.4 equiv.) Was added to the mixture.After the addition of tetrahydrofuran was added Pd (0.05 equiv).The mixture was stirred at reflux at a temperature of 80 .Will try to isolate the crystalline compound H, compound K and byproduct mixture.The resultant was passed through the column with dichloromethane and hexane to obtain the compound L.
5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole[ No CAS ]
C48H28N2O2S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium carbonate; palladium; In tetrahydrofuran; water; toluene;Inert atmosphere; Reflux;
In N2Gas purification system, the compound H is dissolved in toluene, adding the compound F (2.4 eq).Will be dissolved in deionized water K2CO3(8.8 equiv.) Was added to the mixture.In tetrahydrofuran was added, add Pd (0.1 eq).The mixture was stirred at reflux at a temperature of 80 .The mixture was extracted and recrystallized to isolate H, F and compound byproduct compounds.The resultant was passed through the column with dichloromethane and hexane to obtain Compound 2.
With potassium carbonate; palladium; In tetrahydrofuran; water; toluene;Inert atmosphere; Reflux;
In N2Gas purification system, Compound I was dissolved in toluene, adding the compound G (2.4 eq).Will be dissolved in deionized water K2CO3(8.8 equiv.) Was added to the mixture.In tetrahydrofuran was added, add Pd (0.1 eq).The mixture was stirred at reflux at a temperature of 80 .The mixture was extracted and recrystallized to isolate the compound I, G and byproduct compounds.The resultant was passed through the column with dichloromethane and hexane to obtain Compound 8.
5,5'-(sulfonylbis(4,1-phenylene))bis(10,10-diphenyl-5,10-dihydrodibenzo[b,e][1,4]azasiline)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46%
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 24h;
Well-dried 100 mL three-necked round bottom flask charged with 4,4'-sulfonylbis (bromobenzene) (0.7 g, 1.86 mmol), 10,10-diphenyl-5,10-dihydrodibenzo [b, e] [1,4] azasiline (1.43 g, 4.1 mmol), Na-t-butoxide (0.36 g, 3.72mmol), tris (tertbutyl) phosphine (0.04 g, 0.19 mmol) and Pd2(dba)3 (0.09 g) were dissolved in 20 ml of toluene was stirred for 24 hours at 110C . After completion of the reaction was poured into water, and extracted three times with chloroform. The extracted organic layer was dried using MgSO4, the solvent was removed using a rotary evaporator, and separated by column chromatography using EA / n-Hexane (1/3) to obtain the compound 1.7 g (yield = 46%).
9',9''''-(sulfonylbis(4,1-phenylene))bis(3,3'',6,6''-tetra-tertbutyl-9'H-9,3':6',9''tercarbazole)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49%
With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane; In toluene; for 72h;Inert atmosphere; Reflux;
General procedure: DCz (1.24 g, 1.73 mmol), CuI (0.057 g, 0.30 mmol), K3PO4 (0.63 g,3.0 mmol), (±)-trans-1,2-dimethylcyclohexane (123.0 mL, 1.0 mmol) and bis(4-bromophenyl) (phenyl)phosphine oxide (0.33 g,0.75 mmol) was dissolved in 100 mL toluene, then the mixture wasstirred for 72 h under reflux in argon atmosphere. The cooledmixture was extracted with CH2Cl2 (3 100.0 mL) and dried overNa2SO4. The crude product was purified by column chromatographyeluting with petroleum ether-dichloromethane-methanolmixtures to give a white solid (0.60 g, 46.5%).
4-(4-((4-bromophenyl)sulfonyl)phenyl)dibenzothiophene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
48%
The fourth intermediate <strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (4.92 g, 13.16 mmol) andDibenzothiophene-4-boronic acid (2.00 g, 8.77 mmol) was added to a three-neck bottle.Dissolve in 50 mL of tetrahydrofuran (THF), add 8.7 mL of 2M K2CO3 aqueous solution, stir with argon gas for 30 min, and add 0.10 g of Pd(PPh3)4.Heat to 75 C for 16 h. After the reaction solution is cooled to room temperature,Add 30 mL of ethanol and spin dry in a rotary evaporator.The crude product was purified by silica gel column chromatography eluting with a mixture of n-hexane and methylene chloride in a volume ratio of 4:5. The obtained solid was white powder after vacuum drying. The mass was 2.01 g and the yield was 48%. .
The 4-benzoyl-4'-bromobiphenyl (0.11 g, 0.3 mmol), 9, 10 - dihydro - 9, 9 - diphenyl acridine (0.23 g, 0 . 66 mmol), tri-tert-butylphosphonium tetrafluoroboronate (0.02 g), sodium tert-butoxide(0.2 g) adding 100 ml three-neck bottle in, vacuum replace the nitrogen three times, added into the dry toluene after 20 ml. Stir at room temperature 15 min, adding Pd2(dba)3(0.02 G), 120 C under stirring 18 h. Ling actually to the room temperature, over-elution column (for eluting DCM), turns on lathe does, [...] powder sample, carrying out column chromatography separation, to obtain white solid 0.21 g (Y=79%).
8,8-dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-8H-indolo[3,2,1-de]acridine[ No CAS ]
C54H40N2O2S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; at 80℃;Inert atmosphere;
<strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (10 g, 26.6 mmol), Intermediate 1-4 (26.1 g, 63.82 mmol),Potassium carbonate (K2CO3) (32.4 g, 234 mmol), tetrakistriphenylphosphine palladium (0.1 g),Compound 2 (17 g, 82%) was obtained using the same procedure as Compound 1. Compound 1-5 (15 g, 32.44 mmol), toluene (350 ml), under nitrogenCompound 1-4 (15.94 g, 38.93 mmol) was added.Calcium carbonate (K2CO3) (19.7 g, 142.74 mmol), adding deionized water to the reaction mixture,Tetrahydrofuran (200 ml), tetrakistriphenylphosphine palladium (0.1 g) was added, and the mixture was stirred, and the reaction was refluxed at 80 C.After extraction, it was recrystallized from dichloromethane / n-hexane to give Compound 1 (13.5 g, 63%).
9,9,9',9'-tetramethyl-9,10-dihydro-9'H-2,10'-biacridine[ No CAS ]
C72H62N4O2S[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
36%
With tris-(dibenzylideneacetone)dipalladium(0); tert-butylphosphine; sodium t-butanolate; In toluene; for 24h;Reflux; Inert atmosphere;
Add in 100mL two-port bottle2,10'-biguanidine (255mg, 0.6116mmol),<strong>[2050-48-8]4,4'-dibromodiphenyl sulfone</strong> (100 mg, 0.2659 mmol),Tri-tert-butylphosphine (6.4560 mg, 31.91 mumol),Sodium tert-butoxide (102 mg, 1.0621 mmol),Tris(dibenzylideneacetone)dipalladium (14.6 mg, 15.95 mumol)And toluene (60mL),The mixture was refluxed under nitrogen for 24 h.After the reaction solution is cooled to room temperature,The mixture was extracted with CH 2 Cl 2 (3×30 mL);The organic layer was washed successively with water (50 mL).dry,The solvent was distilled off under reduced pressure.Residues with petroleum ether:Dichloromethane (V: V = 2: 1) is eluted by column chromatography.Green solid 100 mg (yield: 36%).
1-bromo-3-((4-bromophenyl)sulfonyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52 mg; 14 mg
2.1) Diels- Alder reaction of 3-bromofuran with divinylsulfone (0166) In a carousel tube fitted with a PTFE septum screw cap divinylsulfone (1.0 g, 8.46 mmol) was weighted. Then, 3-bromofuran (6.3 g, 42.9 mmol) and pyridine (3 mL) were added. The reaction mixture was stirred at 80C during 24 h and was monitored by NMR analysis. The conversion is 95 % to an endo/exo mixture of Diels- Alder adducts. (0167) The reaction mixture was concentrated in vacuo and purified by flash chromatography on silica gel (eluent: cyclohexane/ethyl acetate) to give a near quantitative yield (3.48 g) of a brown oil. (0168) 2.2) Conversion of the Diels- Alder adducts previously obtained to 4,4'- dibromodiphenylsulfone (0169) In a Schlenk tube under argon atmosphere, potassium hydroxide, ca. 85% (0170) (35 mg, 0.53 mmol) is weighted and a solution of the previously obtained brown oil (215 mg, 0.52 mmol) in DMSO (1.5 mL) is added. The reaction mixture was stirred at 100C during 2.5 h. The reaction was monitored by NMR and GC analysis which shows the complete conversion of Diels- Alder adducts to dibromodiphenylsulfone after 1 h. (0171) Gaz chromatography titration shows that the final mixture contains 52 mg of 4,4'-dichlorodiphenylsulfone and 14 mg of 3,4'-dichlorodiphenylsulfone, giving a yield of these two products of 34% in this second step and a 4,4'- dibromodiphenylsulfone / 3,4'- dibromodiphenylsulfone ratio of 79/21.
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate; at 180℃; for 48h;Inert atmosphere;
Add compound 17 (2 g, 5.3 mmol), compound 2 (2.08 g, 10.6 mmol), cuprous iodide (0.1 g, 0.53 mmol) in a 25 ml single-necked flask.K2CO3 (1.30 g, 13.25 mmol) and 18-crown-6 (0.14 g, 0.53 mmol) were dissolved in 10 mL of MPU solution. Under the protection of N2, the temperature was raised to 180 C and the reaction was carried out for 48 h.After the reaction was terminated, it was cooled to room temperature, extracted, and dried, dichloromethane: methanol 10:1 over column, yield: 65%.
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate; at 180℃; for 48h;Inert atmosphere;
Add compound 17 (2 g, 5.3 mmol), compound 24 (2.08 g, 10.6 mmol), cuprous iodide (0.1 g, 0.53 mmol) in a 25 ml single-necked flask.K2CO3 (1.30 g, 13.25 mmol) and 18-crown-6 (0.14 g, 0.53 mmol) were dissolved in 10 mL of MPU solution. Under the protection of N2, the temperature was raised to 180 C and the reaction was carried out for 48 h.After the reaction was terminated, it was cooled to room temperature, extracted, and dried, dichloromethane: methanol 15:1 over column, yield: 70%.
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate; at 180℃; for 48h;Inert atmosphere;
Add compound 17 (2 g, 5.3 mmol), compound 42 (2.08 g, 10.6 mmol), cuprous iodide (0.1 g, 0.53 mmol) in a 25 ml single-necked flask.K2CO3 (1.30 g, 13.25 mmol) and 18-crown-6 (0.14 g, 0.53 mmol) were dissolved in 10 mL of MPU solution. Under the protection of N2, the temperature was raised to 180 C and the reaction was carried out for 48 h.After the reaction was terminated, it was cooled to room temperature, extracted, and dried, dichloromethane: methanol 15:1 over column, yield: 60%.
With tris-(dibenzylideneacetone)dipalladium(0); di-tert-butyl(neopentyl)phosphine; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;
Compound B was obtained by conducting the same synthetic method of Compound B in the synthesis of Compound 11. Under an argon (Ar) atmosphere, Compound B (3.16 g, 8.0 mmol), 1,1?-sulfonylbis[4-bromobenzene] (1.50 g, 4.0 mmol), Pd2(dba)3 (0.183 g, 0.20 mmol), (tBu)3P (0.162 g, 0.80 mmol) and sodium tert-butoxide (0.769 g, 8.0 mmol) were added to toluene (16 mL) in a 100 mL three neck flask, and the mixture was stirred at 80 C. for about 12 hours. After cooling in the air, water was added thereto, an organic layer was separated and taken, and solvent was evaporated under reduced pressure. The crude product thus obtained was purified by silica gel column chromatography to obtain 1.81 g (yield 45%) of Compound 49 as a white solid. The molecular weight of Compound 49 measured by FAB-MS was 1,004. The chemical shift values of the compound measured by 1H-NMR were [7.62 (4H), 7.37-7.28 (32H), 7.18 (4H), 7.01 (4H)]. From the results, the white solid compound was identified as Compound 49.
4-bromo-4‘-thianthrene-1-yl-diphenylsulfone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With bis-triphenylphosphine-palladium(II) chloride; potassium hydroxide; In tetrahydrofuran; water; at 80℃; for 3h;Inert atmosphere;
general procedure for Suzuki cross-coupling reaction. Adried 100 mL flask was charged with 1-thianthrenyl boronic acid (1.0equiv.), bromoaryl derivative (1.0 equiv.), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2, 0.05 equiv.), and powderedpotassium hydroxide (5 equiv.). The reaction vessel was vacuumed andfiled with argon. Degassed tetrahydrofuran (THF) and degassed waterwere added, and the reaction mixture was stirred at 80 C for 3 h. Thecrude product was extracted into DCM, and the organic phase waswashed with water and dried over Na2SO4. The solvent was removedand the residue was purified by column chromatography using hexane/ethyl acetate (6/1) as eluent. The target product was crystallized fromthe eluent.4-Bromo-4?-thianthrene-1-yl-benzophenone (Br-BP-TA) was preparedby method A from 1-thianthrenyl boronic acid (0.38 g, 1.47 mmol),4,4?-dibromobenzophenone (0.50 g, 1.47 mmol), Pd(PPh3)2Cl2 (0.05 g,0.07 mmol), KOH (0.41 g, 7.35 mmol), 10 mL of THF and 2 mL of waterwere used. The yield of white crystals (fw=474 g/mol,mp=138-139 C) was 76%.1H NMR (400 MHz, CDCl3), delta (ppm): 7.82 (d, J=8.2 Hz, 2H, Ar),7.69 (d, J=8.5 Hz, 2H, Ar), 7.60 (d, J=8.5 Hz 2H, Ar), 7.42-7.50 (m,4H, Ar), 7.30 (dd, J=7.5, 1.4 Hz, 1H, Ar), 7.10-7.26 (m, 4H, Ar).13C NMR (100 MHz, CDCl3), delta (ppm): 195.23, 144.59, 141.29,136.35, 136.32, 136.21, 136.07, 135.51, 134.90, 131.72, 131.59,129.92, 129.62, 129.07, 128.89, 128.84, 128.62, 127.97, 127.70,127.61, 127.28.IR numax in cm-1: (CH Ar) 3087, 3068, 3051; (C=O) 1647; (C=CAr) 1480; (CH Ar) 929, 857; (CS) 746; (CBr) 634.MS (APCI+, 20V), m/z (%): 475 ([M+H]+, 100)Elemental analysis. Calcd. for C25H15BrOS2 (%): C 63.16, H 3.18, Br16.81, O 3.37, S 13.49. Found (%): C 63.17, H 3.23, O 3.44.
With tetrakis(triphenylphosphine) palladium(0); tricaprylylmethylammonium chloride; sodium carbonate; In tetrahydrofuran; water; for 30h;Inert atmosphere; Reflux;
Under argon atmosphere,In a reaction vessel, 2.0 g of a compound represented by formula (I-2-1),1.3 g of a compound represented by the formula (I-2-2)2.9 g of a compound represented by formula (I-2-3),1.3 g sodium carbonate, 12 mL water,30 mL of tetrahydrofuran,Aliquot 336 (manufactured by Aldrich) 0.3 g,0.1 g of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 30 hours.It was diluted with dichloromethane and separated.After washing the organic layer twice with water,Purification was performed by column chromatography (silica gel, chloroform). Preparative thin layer chromatography (silica gel, 2 mm thick,Hexane / ethyl acetate (3: 1),Purification is carried out by column chromatography (silica gel, toluene) and recrystallization (toluene / ethanol).0.3 g of a compound represented by the formula (I-2) was obtained.
3-(9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren -2-yl)-9-phenyl-9H-carbazole[ No CAS ]
3-(7-(4-((4-bromophenyl)sulfonyl)phenyl)-9,9-dioctyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
41%
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
General procedure: (9-phenyl-9H-carbazol-3-yl)boronic acid (2.87g, 0.010 mol), 2,7-dibromo-9,9-dioctyl-9H-fluorene (6.58 g, 0.012 mol), PdCl2(PPh3)2 (0.1g), H2O (5 ml) and K2CO3 (6g, 0.043 mol) were added to a 250 ml flaskwith 40 ml THF. The mixture was heated at 78 C under argon atmospherefor 12h. After cooling down, the resulting mixture was extractedwith CH2Cl2, and the organic layer was collected and dried with MgSO4.The solvent was removed and purified by silica gel chromatography toobtain white solid, yield 95% (6.74 g).
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
Compound 2a (1.1.516 g, 0.002 mol), bis(4-phenyl)thiophenol (1.13 g, 0.003 mol), Pd(PPh3)2Cl2 (0.1 g), K2CO3 (1 g, 0.007 mol),H2O (5ml),THF (20 ml) was successively added to a three-necked flask, and the mixture was vacuumed under nitrogen and heated to 78 C to reflux for 12 h.After the reaction was completed, it was cooled to room temperature, extracted with DCM and dried over anhydrous magnesium sulfate.Over the elution column (DCM elution), remove the solvent by rotary evaporation, and add silica gel powder to prepare.Separated by the column. A white solid was obtained.
9-(4-(9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl)phenyl)-9H-carbazole[ No CAS ]
[ 2050-48-8 ]
9-(4-(7-(4-((4-bromophenyl)sulfonyl)phenyl)-9,9-dioctyl-9H-fluoren-2 -yl)phenyl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
General procedure: (9-phenyl-9H-carbazol-3-yl)boronic acid (2.87g, 0.010 mol), 2,7-dibromo-9,9-dioctyl-9H-fluorene (6.58 g, 0.012 mol), PdCl2(PPh3)2 (0.1g), H2O (5 ml) and K2CO3 (6g, 0.043 mol) were added to a 250 ml flaskwith 40 ml THF. The mixture was heated at 78 C under argon atmospherefor 12h. After cooling down, the resulting mixture was extractedwith CH2Cl2, and the organic layer was collected and dried with MgSO4.The solvent was removed and purified by silica gel chromatography toobtain white solid, yield 95% (6.74 g).
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
Compound 2b (1.516 g, 0.002 mol),Bis(4-phenyl)thiophenol (1.13 g, 0.003 mol), Pd(PPh3)2Cl2 (0.1 g), K2CO3 (1 g, 0.007 mol), H2O (5 ml),THF (30 ml) was successively added to a three-necked flask, and the mixture was vacuumed under nitrogen and heated to 78 C to reflux for 12 h.After the reaction was completed, it was cooled to room temperature, extracted with DCM and dried over anhydrous magnesium sulfate.Over the elution column (DCM elution), remove the solvent by rotary evaporation.Add silica gel powder and sample through the column. A white solid was obtained.
4-(9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl)-N,N-diphenylaniline[ No CAS ]
[ 2050-48-8 ]
4-(7-(4-((4-bromophenyl)sulfonyl)phenyl)-9,9-dioctyl-9H-fluoren-2-yl)-N,N-diphenylaniline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
General procedure: (9-phenyl-9H-carbazol-3-yl)boronic acid (2.87g, 0.010 mol), 2,7-dibromo-9,9-dioctyl-9H-fluorene (6.58 g, 0.012 mol), PdCl2(PPh3)2 (0.1g), H2O (5 ml) and K2CO3 (6g, 0.043 mol) were added to a 250 ml flaskwith 40 ml THF. The mixture was heated at 78 C under argon atmospherefor 12h. After cooling down, the resulting mixture was extractedwith CH2Cl2, and the organic layer was collected and dried with MgSO4.The solvent was removed and purified by silica gel chromatography toobtain white solid, yield 95% (6.74 g).
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 78℃; for 12h;Inert atmosphere;
Compound 2c (1.516 g, 0.002 mol),Bis(4-phenyl)thiophenol (1.13 g, 0.003 mol), Pd(PPh3)2Cl2 (0.1 g), K2CO3 (1 g, 0.007 mol), H2O (5 ml), THF (30 ml)The flask was placed in a three-necked flask, vacuumed under nitrogen, and heated to 78 C for 12 h.After the reaction was completed, it was cooled to room temperature, extracted with DCM and dried over anhydrous magnesium sulfate.Over the elution column (DCM elution), remove the solvent by rotary evaporation, and add silica gel powder to prepare.Separated by the column. A white solid was obtained.
With cadmium(II) sulfate crystallohydrate; phosphorus pentoxide; at 20℃; for 5h;Milling; Sealed tube; Green chemistry;
General procedure: For all of the experiments, a stainless milling beaker of 2.5 mL along with one stainless milling ball (d = 6.0 mm) was used. The mechanochemical reaction was performed in a MM400 mixer mill at room temperature. A mixture of arene (15.4 mg, 0.1 mmol), 3CdSO4·xH2O (73 mg, 0.35 mmol), and P2O5 (156 mg, 1.1 mmol) were added to the stainless milling beaker (2.5 mL), along with one stainless milling ball (d = 6.0 mm). The beaker was sealed and placed in the mixer mill. The reaction was performed at 28 Hz for 5 hours at room temperature. Subsequently, the reaction mixture was dissolved in chloroform (20 mL). The resulting mixture was filtered to remove the undissolved residue, and then the solvent was removed via rot-vap under vacuum followed by purification through column chromatography to afford the product. The product was dissolved in a proper deuterium reagent with 7 mul of dibromomethane. The components were analyzed and determined by 1H NMR and literature.
With NBS; sulfuric acid; glacial acetic acid at 60℃; for 5h;
4 Example 3
General procedure: 1 mmol of compound I obtained in Example 1 was dissolved in 4 ml of glacial acetic acid, 1.2 ml of concentrated sulfuric acid was added dropwise, and the temperature was raised to 60°C, 1 mmol of N-bromosuccinimide was added and reacted for 5 hours to obtain 2-diphenylphosphorylphenyl 4-bromophenyl sulfone
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