* 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 ammonium acetate In water at 20 - 40℃; for 3 h;
[0024] 120 ml of distilled water was added to 1,092 g (14.2 mol, 4.0 eq.) of ammonium acetate at 40[deg.] C., and 500 g of 20 wt percent aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. Immediately after the addition was finished, the reaction mixture was neutralized with distilled water so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 82.0 g (53.2percent yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97percent.
50.9%
Stage #1: With ammonium acetate In water at 20 - 40℃; for 8 h; Stage #2: With ammonia In water
Example 1 130 ml of distilled water was added to 709 g of ammonium acetate (9.2 mol, 2.67 eq.) at 40° C., and 500 g of 20 wt percent aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. The resulting reaction mixture was additionally stirred for five hours at room temperature. The reaction mixture was then neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered and then washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 78.4 g (50.9percent yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97percent.
45.8%
Stage #1: With ammonium acetate In water at 20 - 40℃; for 8 h; Stage #2: With sodium hydroxide In water
[0021] The same amount of glyoxal as in Example was reacted with ammonium acetate in the same manner as described in Example 1. The reaction mixture was then neutralized with 5percent aqueous sodium hydroxide, instead of aqueous ammonia, to obtain 70.6 g (45.8percent yield) of the desired product.
44.6%
Stage #1: With ammonium formate In water at 50℃; for 1.5 h; Stage #2: With ammonia In water
Example 3 130 ml of distilled water was added to 580 g (9.2 mol, 2.67 eq.) of ammonium formate at 50° C., and 500 g of 20 wt percent aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for one and a half hours while vigorously stirring. Immediately after the addition was finished, the reaction mixture was neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 68.7 g (44.6percent yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97percent.
43.1%
Stage #1: With ammonium benzoate In water at 20 - 40℃; for 4 h; Stage #2: With ammonia In water
Example 4 130 ml of distilled water was added to 959 g (6.9 mol, 2.0 eq.) of ammonium benzoate at 40° C., and 500 g of 20 wt percent aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. The resulting reaction mixture was then additionally stirred for one hour at room temperature. The reaction mixture was then neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 66.4 g (43.1percent yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97percent.
Reference：
[1] Patent: US2003/199700, 2003, A1, . Location in patent: Page/Page column 2
[2] Patent: US2003/199700, 2003, A1, . Location in patent: Page/Page column 2
[3] Archiv der Pharmazie, 1986, vol. 319, # 2, p. 183 - 185
[4] Patent: US2003/199700, 2003, A1, . Location in patent: Page/Page column 2
[5] Patent: US2003/199700, 2003, A1, . Location in patent: Page/Page column 2
[6] Patent: US2003/199700, 2003, A1, . Location in patent: Page/Page column 2
[7] Organic Letters, 2004, vol. 6, # 21, p. 3845 - 3847
[8] Zeitschrift fur Anorganische und Allgemeine Chemie, 2012, vol. 638, # 9, p. 1278 - 1286
[9] Bulletin of the Chemical Society of Japan, 1995, vol. 68, # 7, p. 1753 - 1774
[10] Journal of Materials Chemistry C, 2017, vol. 5, # 14, p. 3519 - 3527
[11] Canadian Journal of Chemistry, 2009, vol. 87, # 6, p. 729 - 737
[12] Journal of Heterocyclic Chemistry, 2002, vol. 39, # 4, p. 733 - 735
[13] Organic Letters, 2018, vol. 20, # 12, p. 3613 - 3617
[14] Journal of Organic Chemistry, 1989, vol. 54, # 13, p. 3057 - 3061
[15] Australian Journal of Chemistry, 1994, vol. 47, # 4, p. 723 - 738
[16] Journal of the American Chemical Society, 2003, vol. 125, # 16, p. 4951 - 4957
[17] Journal of Fluorine Chemistry, 2009, vol. 130, # 6, p. 522 - 527
[18] Patent: WO2005/26178, 2005, A2, . Location in patent: Page/Page column 77; Sheet 31
[19] Bulletin of the Korean Chemical Society, 2012, vol. 33, # 11, p. 3645 - 3650
[20] New Journal of Chemistry, 2013, vol. 37, # 11, p. 3706 - 3715
[21] RSC Advances, 2014, vol. 4, # 44, p. 23116 - 23124
[22] Australian Journal of Chemistry, 2015, vol. 68, # 10, p. 1513 - 1517
[23] Chemistry - A European Journal, 2016, vol. 22, # 6, p. 2108 - 2113
[24] Catalysis Letters, 2016, vol. 146, # 4, p. 841 - 850
[25] European Journal of Inorganic Chemistry, 2017, vol. 2017, # 12, p. 1764 - 1771
2
[ 93241-62-4 ]
[ 492-98-8 ]
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[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1987, vol. 23, # 8, p. 854 - 856[2] Khimiya Geterotsiklicheskikh Soedinenii, 1987, # 8, p. 1069 - 1070
3
[ 106536-97-4 ]
[ 492-98-8 ]
Reference：
[1] Synthesis, 1986, # 4, p. 336 - 337
4
[ 131543-46-9 ]
[ 631-61-8 ]
[ 492-98-8 ]
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[1] New Journal of Chemistry, 2015, vol. 39, # 3, p. 1827 - 1839
[2] Justus Liebigs Annalen der Chemie, 1918, vol. 416, p. 231
[3] Justus Liebigs Annalen der Chemie, 1927, vol. 456, p. 259,269,270,271
[4] Chemistry of Heterocyclic Compounds, 2017, vol. 53, # 6-7, p. 697 - 701[5] Khim. Geterotsikl. Soedin., 2017, vol. 53, # 6-7, p. 697 - 701,5
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[ 131543-46-9 ]
[ 107-21-1 ]
[ 492-98-8 ]
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[1] Journal of Materials Chemistry C, 2016, vol. 4, # 17, p. 3726 - 3737
6
[ 3039-13-2 ]
[ 492-98-8 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1987, vol. 23, # 8, p. 854 - 856[2] Khimiya Geterotsiklicheskikh Soedinenii, 1987, # 8, p. 1069 - 1070
7
[ 496-45-7 ]
[ 492-98-8 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1987, vol. 23, # 8, p. 854 - 856[2] Khimiya Geterotsiklicheskikh Soedinenii, 1987, # 8, p. 1069 - 1070
8
[ 106536-97-4 ]
[ 492-98-8 ]
[ 106536-98-5 ]
Reference：
[1] Synthesis, 1986, # 4, p. 336 - 337
9
[ 599-01-9 ]
[ 492-98-8 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1918, vol. 416, p. 231
[2] Journal of the Chemical Society, 1887, vol. 51, p. 553
[3] Chemische Berichte, 1884, vol. 17, p. 1998[4] Chemische Berichte, 1887, vol. 20, p. 2345 Anm.
10
[ 131543-46-9 ]
[ 288-32-4 ]
[ 492-98-8 ]
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[1] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1875, vol. 7, p. 254
[2] Chemische Berichte, 1876, vol. 9, p. 1544[3] Chemische Berichte, 1877, vol. 10, p. 1366
[4] Justus Liebigs Annalen der Chemie, 1858, vol. 107, p. 199
[0024] 120 ml of distilled water was added to 1,092 g (14.2 mol, 4.0 eq.) of ammonium acetate at 40[deg.] C., and 500 g of 20 wt % aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. Immediately after the addition was finished, the reaction mixture was neutralized with distilled water so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 82.0 g (53.2% yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97%.
50.9%
Example 1 130 ml of distilled water was added to 709 g of ammonium acetate (9.2 mol, 2.67 eq.) at 40 C., and 500 g of 20 wt % aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. The resulting reaction mixture was additionally stirred for five hours at room temperature. The reaction mixture was then neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered and then washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 78.4 g (50.9% yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97%.
45.8%
[0021] The same amount of glyoxal as in Example was reacted with ammonium acetate in the same manner as described in Example 1. The reaction mixture was then neutralized with 5% aqueous sodium hydroxide, instead of aqueous ammonia, to obtain 70.6 g (45.8% yield) of the desired product.
44.6%
Example 3 130 ml of distilled water was added to 580 g (9.2 mol, 2.67 eq.) of ammonium formate at 50 C., and 500 g of 20 wt % aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for one and a half hours while vigorously stirring. Immediately after the addition was finished, the reaction mixture was neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 68.7 g (44.6% yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97%.
43.1%
Example 4 130 ml of distilled water was added to 959 g (6.9 mol, 2.0 eq.) of ammonium benzoate at 40 C., and 500 g of 20 wt % aqueous glyoxal (3.45 mol) was then slowly added dropwise to the resulting slurry for three hours while vigorously stirring. The resulting reaction mixture was then additionally stirred for one hour at room temperature. The reaction mixture was then neutralized with aqueous ammonia so as to adjust pH to 5-7. The produced brown colored solid was filtered, and washed alternately with 500 ml of acetone and 500 ml of distilled water several times, to obtain 66.4 g (43.1% yield) of 2,2'-bi-1H-imidazole having a purity of not less than 97%.
With ammonia; In water; at 0℃; for 7h;
To 25 mL of glyoxal (40 wt % in water) was added 25 mL of water. The reaction mixture was cool in an ice-bath and ammonia gas was bubbled slowly through the mixture for 7 hours. The reaction mixture was filtered to give 710 mg of bidiimdazole (compound 45) as a gray colored powder. This was used in the next step without further purification, LC/MS M+H 135.0.
With ammonium acetate; In water; at 40℃;
2,2'-Biimidazole was synthesized according to a reportedprocedure.[9] In a typical reaction, aqueous glyoxal (23.0 mL,40 wt-%) was added dropwise to a vigorously stirred solution ofammonium acetate (70.0 g) and H2O (13.0 mL) at 408C over aperiod of 4 h. After completion of the reaction, the crude product(4.44 g, 54.15 %) was filtered and washed several times withwater and acetone. The product was then further purified byliquid anti-solvent crystallization and dried overnight undervacuum before use and analysis. dH ([D6]DMSO) 7.08(d, 4H), 12.65 (s, 2H). m/z (ESI-MS) 135.0751; calcd forC6H7N4, 135.0609 [M].
With ammonium chloride; In water; at 20 - 45℃; for 7h;
A round-bottomed flask was charged with ammonium chloride (49.2 g, 0.92 mol) and water (30 mL). An aqueous (40 wt%) solution of glyoxal (16 mL, 0.14 mol) was then added dropwise over a period of 3 h at 45 C. The mixture was stirred for an additional 4 h at room temperature. After the reaction was complete, the pH was adjusted to six by addition of an aqueous solution of potassium hydroxide. The resultant brownish solid was separated from the aqueous mother liquor by filtration, washed with an excess of water and acetone (4 9 10 mL), and vacuum-dried (1.1 g, 18 %). To purify the organic ligand, the crude product was dissolved in 20 mL of boiling ethylene glycol, followed by addition of charcoal (1 g). The hot solution was filtered off and cooled to room temperature. The resultant colourless needles of H2biim were isolated, washed, and vacuum-dried. Anal. Calcd for C6H6N4 (134.14): C, 53.72; H, 4.50; N, 41.76. Found: C, 53.35; H, 4.29; N, 41.58. Selected FT-IR (cm-1): nu = 3174w, 3141m, 3072m, 3000s, 2892s, 2803vs, 2746m, 2634m, 1544s, 1434m, 1403vs, 1332s, 1216m, 1143w, 1105vs, 939s, 914m, 885s, 829m, 761s, 746s, 688s, 615w. 13C{1H} CP MAS NMR: delta = 118.2, 120.3 (C5,C5'), 126.4, 128.7 (C4,C4'), 138.8 (C2,C2'). The NMR data are in agreement with that reported previously [59].
With ammonium acetate; In water; at 20℃; for 4h;
The 2,2'-biimidazole ligand was synthesized according to a reported procedure [83]. In a typicalreaction, aqueous glyoxal (23.0 mL, 40 wt%) was added dropwise to a vigorously stirred solution of ammonium acetate (70.00 g) and H2O (23.0 mL) at room temperature over a period of 4 h. After completion of the reaction, the product was filtered and washed several times of water and acetone. deltaH ([D6] DMSO)7.08 (d, 4H), 12.68 (s, 2H).
With ammonium hydroxide; at 45℃; for 2h;
L1A. 1H,1?H-2,2?-biimidazole (L1A) was obtained following belowprocedure [20]. Aqueous glyoxal (20%) was placed in water bath at 45C, then ammonia was bubbled into this solution for 2 h. The mixturewas further stirred overnight. Solid product was collected, washedwith water and then dissolved in ethylene glucol. After being decolorizedby C powder, the solutionwas cooled.White solid product was obtainedas L1A. 1H NMR (DMSO d6): delta 7.08 (s).
To 60 mg (0.44 mmol) of biimidazole was added 1 mL of anhydrous DMF. The reaction mixture was cooled in an ice-bath and 27 mg (0.67mmol) of NaH (60% in oil) was added. The reaction mixture was allowed to stir at 0C for 1 hour. 140 muL (0.92 mmol) of methyl p-toluene sulfonate was added and the reaction mixture was allowed to stir an additional lh at 0C and then two days at room temperature. The reaction mixture was concentrated and purified by silica gel column chromatography using 50% ethyl acetate in methanol to give 60 mg (0.36 mmol, 83%) of dimethyl biimidazole (compound 46), LC/MS M+H 163.1
Multi-step reaction with 2 steps
1.1: NaH / dimethylformamide / 1 h / 0 °C
1.2: 40 percent / dimethylformamide / 0 - 20 °C
2.1: NaH / dimethylformamide / 1 h / 20 °C
2.2: 98 percent / NaI / dimethylformamide / 24 h / 80 °C
A solution of (No.5-Ind) Mo (CO) 2 (n3-C3Hs) (0.25g, 0. 81mmol) in CH2CI2 was treated with HBF4. Et2O (1 eq. ). After 10 minutes dme was added in excess and the reaction was left for 15 minutes. 0.13 g (1 mmol) of 2,2'-bis-imidazol were added and the reaction was left for 2 hours at room temperature. After concentration to about 5 ml and addition of Et2O, an orange complex precipitated. The mixture was filtered and the residue recrystallized from CH2Cl2/Et20 (No. = 90%). A drawing of the structure and physical data are given in Table 1.
[Cd3(biphenyl-2,2',4,4'-tetracarboxylate)(1H-2,2'-biimidazole(-1H))2(1H,1'H-2,2'-biimidazole)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
16.6%
With NaOH In water High Pressure; under hydrothermal conditions; mixt. of biphenyltetracarboxylic acid, Cdsalt, biimidazole, NaOH and H2O heated at 160°C for 3 d; cooled slowly to room temp. (5°C/h); filtered; crystals washed with H2O; dried in air; elem. anal.;
Synthetic example 11 :1 ,r-bis(4-bromobenzyl)-1H,1 'H^'-biimidazole11To a mixture of 1H,1 W-<strong>[492-98-8]2,2'-biimidazole</strong> (2.1 g, 15.7 mmol) in DMF at 0 "C was added NaH (1.32 g of a 60% dispersion in mineral oil, 32.8 mmol). The mixture was allowed to warm to room temperature and stirred for 30 min. 1-bromo-4- (bromomethyl)benzene (11.7 g, 46.8 mmol) was added and the mixture was heated to 80 "C and stirred (2h). The mixture was cooled to room temperature and saturated aqueous NH4CI (2 mL) was added and the mixture was concentrated. The mixture was diluted with CH2CI2 and Eta20 and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2 0:100 then 50:50 then 80:20) to give l .l'-bisi^bromobenzy -I ^^'-biimidazole (4.12 g, 56%) as a colourless solid. 1H NMR (CDCI3) 400 MHz) delta 5.66 (s, 4H), 6.86 -.6.91 (m, 4H), 6.93 (d( J 1.2 Hz, 2H), 7.11 (d, J 1.2 Hz, 2H), 7.33 - 7.39 (m, 4H); 13C NMR (CDCI3, 100 MHz) 5 50.2, 121.5, 121.7, 128.5, 129.1 , 131.8, 136.3, 138.0; HRMS (El) m/z 469.9741 C2oHi6 4Br2 [M]+" requires 671.2918.
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 2:4,441H 'H-2>2,-biimidazole-1 vdiyl)bis(/Vl/V-diphenylaniline)A mixture of IH.I'H^'-biimidazole (1.02 g, 7.63 mmol), 4-bromo-A/,A/- diphenylaniline (9.89 g, 30.5 mmol) and Cs2C03 (12.4 g, 38.2 mmol) in DMF (150 mL) was degassed (N2 bubbling, 15 min). Cu20 (440 mg, 3.0 mmol) was added and the mixture was heated (140 C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H20 and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/Et-jN/MeOH 100:1 :0 then 100:1 :2 then 100:1:5) to give 4,4'- (1Hl1,H-2,2,-biimidazole-1,r-diyl)bis(A/,A/-diphenylaniline) (1.57 g, 33%) as a colourless solid. A. portion of this material was further purified firstly, by recrystallisation (petrol/toluene) and then by distillation (sublimation apparatus 215 C, 10-6 mBar): m.p. 174 - 182 C (DSC); 1H NMR (CDCI3, 400 MHz) delta 6.67 (d, J 8.8 Hz, 4H), 6.88 (d, J 8.8 Hz, 4H), 7.00 - 7.06 (m, 12H), 7.15 (br s, 2H), 7.18 - 7.25 (m, 8H), 7.34 (br s, 2H); 13C NMR (CDCI3, 100 MHz) delta 121.8, 122.7, 123.8, 124.6, 124.7, 128.9, 129.4, 130.0, 146.9, 147.8; HRMS (El) m/z 619.2598 C 2H3iN6 [M - H]+* requires 619.2605
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 6:1 , 1 ,-bis(4-(pyridin-3-yl)phenyl)-1 H,1 'H-2,2'-biimidazole6A mixture of 1H,1'H-2,2'-biimidazole (950 mg, 7.1 mmol), <strong>[129013-83-8]3-(4-bromophenyl)pyridine</strong> (4.95 g, 21.3 mmol) and Cs2C03 (9.24 g, 28.4 mmol) in DMF (80 mL) was degassed ( 2 bubbling, 15 min). Cu20 (410 mg, 2.9 mmol) was added and the mixture was heated (140 "C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H20 and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2/MeOH 40:60:3 then 35:60:5 then 30:60:10) to give 1 ,1,-bis(4-(pyridin-3-yl)phenyl)-1 H,1'H-2,2'-biimidazole (1.05 g, 34%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/toluene/petrol) and then by distillation (sublimation apparatus 260 DC, 10"6 mBar): m.p. 218 - 223 C (DSC); 1H NMR (CDCI3, 400 MHz) delta 6.95 - 7.00 (m, 4H), 7.15 (d, J 1.2 Hz, 2H), 7.29 (d, J 1.2 Hz, 2H), 7.38 (ddd, J 0.6, 4.8, 7.9 Hz, 2H), 7.40 - 7.45 (m, 4H), 7.82 (ddd, J 0.6, 1.7, 7.9 Hz, 2H), 8.62 (dd, J 1.4, 4.8 Hz, 2H), 8.79 (d. J 1.9 Hz, 2H); 13C NMR (CDCI3, 100 MHz) delta 121.4, 123.7, 124.8, 127.7, 130.2, 134.1 , 135.2, 137.0, 137.2, 137.3, 148.1 , 149.0; HRMS (El) m/z 439.1665 CzeHig e [M - H]+' requires 439.1666.
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 5:1 , 1 '-di(9,9'-spirobi[fluorene]-2-yl)-1 H, 1 'H-<strong>[492-98-8]2,2'-biimidazole</strong>A mixture of 1H,1 mmol), 2-bromo-9,9'- spirobi(fluorene) (3.2 g, 8.1 mmol) and Cs2C03 (4.12 g, 12.6 mmol) in DMF (60 mL) was degassed (N2 bubbling, 15 min). Cu20 (140 mg, 0.98 mmol) was added and the mixture was heated (140 C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H20 and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2/MeOH 40:60:0 then 40:60:2 then 40:60:4) to give l. -d g.g'-spirobilfluorenel^-y -IH.i'H^^'-biimidazole (560 mg, 29%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/toluene) and then by sublimation (320 C, 10"* mBar): m.p. 404 - 412 C (DSC); 1H NMR (CDCI3, 400 MHz) delta 5.84 (d, J 1.9 Hz, 2H), 6.33 (d, J 7.6 Hz, 4H), 6.60 (s, 2H), 6.64 - 6.71 (m, 4H), 6.84 (s, 2H), 6.92 (t, J 7.4 Hz, 4H), 7.14 (t, J 7.4 Hz, 2H), 7.25 (t, J 7.5 Hz, 4H), 7.40 (t, J 7.4 Hz, 2H), 7.49 (d, J 8.2Hz, 2H), 7.72 - 7.80 (m, 6H); 3C NMR (CDCI3, 100 MHz) delta 65.6, 118.2, 120.1 , 120.1 , 120.2, 120.3, 122.1 , 123.8, 124.2, 127.8, 127.9, 128.2, 129.3, 136.0, 136.5, 140.4, 140.6, 141.6, 147.7, 148.8, 150.0; HRMS (El) m/z 761.2662 C56H33N4 [M - Hf requires 761.2700.
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 7: yl)pyridin-2-amine)7A mixture of 1H,17-/-<strong>[492-98-8]2,2'-biimidazole</strong> (840 mg, 6.3 mmol), A/-(4-bromophenyl)-A/- (pyridin-2-yl)pyridin-2-amine (6.59 g, 20.3 mmol) and Cs2C03 (10.14 g, 31.2 mmol) in DMF (70 mL) was degassed (N2 bubbling, 15 min). Cu20 (360 mg, 2.5 mmol) was added and the mixture was heated (140 "C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H20 and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2/MeOH 35:60:5 then 32:60:8 then 28:60:12) to give Lambda/,Lambda ·(4,4'-(1Eta, 1 "H^'-biimidazoie-l , 1 '-diyl)bis(4, 1 -phenylene))bis(A/-(pyridin- 2-yl)pyridin-2-amine) (1.36 g, 35%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/EtOAc/petrol) and then by distillation (sublimation apparatus 260 C, 10~6 mBar): m.p. 218 - 222 C (DSC); 'H NMR (CDCI3l 400 MHz) delta 6.75 - 6.80 (m, 4H), 6.90 (ddd, J 0.8, 4.9, 7.3 Hz, 4H), 6.93 - 7.00 (m, 8H), 7.09 (d, J 1.0 Hz, 2H), 7.26 (s, 2H), 7.52 (ddd, J 2.0, 7.3, 8.3 Hz, 4H), 8.24 (ddd, J 0.7, 1.9, 4.9 Hz, 4H); 13C NMR (CDCI3, 100 MHz) delta 117.0, 118.6, 121.1 , 125.2, 127.5, 130.0, 133.7, 137.6, 144.3, 148.6, 157.7; HRMS (El) m/z 623.2420 C38H27 10 [M - H]+' requires 623.2415.
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 4:1 , 1 '-bis(9-(pyridin- - - H-ca zol- - - ' - ,2'-biimidazoleA mixture of 1 H,1'H-<strong>[492-98-8]2,2'-biimidazole</strong> (800 mg, 6.0 mmol), 3-bromo-9-(pyridin-2-yl)- 9W-carbazole (6.7 g, 20.8 mmol) and Cs2C03 (9.66 g, 29.7 mmol) in DMF (100 mL) was degassed (N2 bubbling, 15 min). Cu20 (340 mg, 2.4 mmol) was added and the mixture was heated (140 'C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H2O and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2/MeOH 40:60:0 then 40:60:3 then 40:60:5) to give 1 ,1^bis(9-(pyridin-2-yl)-9H-carbazol-3-yl)-W (1.44 g, 39%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/toluene/petrol) and then by distillation (sublimation apparatus 280 C, 10"6 mBar): m.p. 215 - 227 C (DSC); 1H NMR (CDCI3, 400 MHz) delta 6.78 (dd, J 2.1 , 8.7 Hz, 2H), 7.02 - 7.12 (m, 4H), 7.18 (d, J 1.9 Hz, 2H), 7.28 - 7.34 (m, 6H), 7.47 (d, J 8.1 Hz, 2H), 7.54 (d, J 8.7 Hz, 2H), 7.60 (d, J 7.5 Hz, 2H), 7.66 (d, J 8.3 Hz, 2H), 7.88 (dt J 2.0, 7.5 Hz, 2H), 8.69 (ddd, J 0.7, 1.9, 4.9 Hz, 2H); 13C NMR (CDCI3> 50 MHz) delta 111.0, 111.3, 115.9, 118.8, 120.0, 121.0, 121.4, 122.4, 123.2, 124.4, 126.7, 129.8, 130.7, 138.1 , 138.5, 139.8, 149.6, 151.2; HRMS (El) m/z 617.2175 C40H25N8 [M - Eta requires 616.2197.
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 72h;Inert atmosphere;
Synthetic example 8:1 ,1 '-bis(4-(1 OH-phenothiazin-10-yl)phenyl)-1 H,1 'H^'-biimidazole8A mixture of 1H,1'H-<strong>[492-98-8]2,2'-biimidazole</strong> (480 mg, 3.6 mmol), 10-(4-bromophenyl)-10H- phenothiazine (3.80 g, 10.8 mmol) and Cs2C03 (5.85 g, 18.0 mmol) in DMF (60 mL) was degassed (N2 bubbling, 15 min). CU2O (210 mg, 1.5 mmol) was added and the mixture was heated (140 C, 72h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H2O and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2CI2/MeOH 40:60:0 then 38:60:2 then 35:60:5) to give 1 ,1'-bis(4-(10H-phenothiazin-10-yl)phenyl)-1H,1'H-2,2,-biimidazole (1.12 g, 46%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/toluene/petrol) and then by distillation (sublimation apparatus 260 C, 10"6 mBar): m.p. 227 - 232 C (DSC); 1H NMR (CDCI3, 400 MHz) delta 6.36 - 6.42 (m, 4H), 6.86 - 6.97 (m, 12H), 7.08 - 7.16 (m, 8H), 7.20 (br s, 2H), 7.35 (br s, 2H); 13C NMR (CDCI3, 100 MHz) delta 118.4, 123.6, 123.8, 125.4, 126.8, 127.4, 128.4, 130.5, 135.2, 141.5, 143.3; HRMS (El) m/z 679.1710 C^Hzr^ [M - Hf requires 679.1733.
1,1'-bis(6-methyl-9-p-tolyl-9H-carbazol-3-yl)-1H,1'H-2,2'-biimidazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
32%
With caesium carbonate;copper(I) oxide; In N,N-dimethyl-formamide; at 140℃; for 96h;Inert atmosphere;
Synthetic example 10:1 , 1 '-bis(6-methyl-9-p-tolyl-9H-carbazol-3-y.)-1 H, 1 ,H-2,2i-biimidazole10A mixture of 1W, W-2,2*-biimidazole (890 mg, 6.6 mmol), 3-bromo-6-methyl-9-p-tolyl- 9H-carbazole (6.49 g, 18.6 mmol) and Cs2C03 (7.55 g, 23.2 mmol) in D F (80 mL) was degassed (N2 bubbling, 15 min). Cu20 (380 mg, 2.7 mmol) was added and the mixture was heated (140 C, 96h). The mixture was allowed to cool to room temperature and filtered through Celite washing with CH2CI2. The combined filtrate and washings were concentrated. The mixture was diluted with CH2CI2 and H2O and the organic phase was separated. The aqueous phase was re-extracted (CH2CI2) and the combined organics were washed (saturated aqueous NaCI), dried (MgS04), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc CH2CI2/ eOH 39:60:1 then 37:60:3 then 35:60:5) to give l.r-bisie-methyl-g-p-tolyl-gH-carbazol-S-y -IH.rH^^'-biimidazole (1.42 g, 32%) as a colourless solid. A portion of this material was further purified firstly, by recrystallisation (CH2CI2/toluene/petrol) and then by distillation (sublimation apparatus 270 C, 1CT6 mBar): m.p. 208 - 214 C (DSC); 1H N R (CDCI3, 400 MHz) delta 2.38 (s, 6H), 2.49 (s, 6H), 6.71 (dd, J 1.8, 8.7 Hz, 2H), 7.03 (d, J 8.6 Hz, 2H), 7.05 - 7.20 (m, 8H), 7.23 - 7.40 (m, 12H); 13C NMR (CDCI3, 100 MHz) 5 21.2, 21.3, 109.4, 109.4, 115.7, 119.7, 121.8, 122.4, 123.1, 126.5, 127.8, 129.3, 129.6, 130.4, 134.6, 137.4, 139.6, 139.7; HRMS (El) m/z 671.2916 C46H35 6 [M - Hf* requires 671.2918
With sodium nitrate; sulfuric acid;urea; at 20 - 80℃; for 6h;
Example 1Synthesis of 4,4',5,5'-tetranitro-<strong>[492-98-8]2,2'-biimidazole</strong> 753 mL of about 95% sulphuric acid and 100 g of biimidazole were placed into a 2 L round bottom flask and biimidazole was all dissolved over one hour. When biimidazole had been all dissolved, 4.48 g of urea was placed thereinto as a catalyst, and subsequently, about 60 g of sodium nitrate was slowly injected in a temperature range of 20 to 30 C. Since yellowish brown gas NOx is generated while injecting sodium nitrate, it may be dangerous to inject at a time, and thus sodium nitrate was slowly injected while maintaining a temperature between 20 and 30 C. After injecting all sodium nitrate, the temperature of the reactor was raised to 80 C. to carry out the reaction for 5 hours, thereby completing the reaction. Next, the temperature of the reactor was lowered to 20 C., and a reaction solution was slowly poured into 1 L of ice water. Solid matter extracted from the ice water was filtered out to obtain 142 g of 4,4',5,5'-tetranitro-<strong>[492-98-8]2,2'-biimidazole</strong> in the state of powder (Yield: 60%).1H-NMR (CDCl3): delta (ppm) 10.58 (br, 2H), 13C-NMR (CDCl3) delta (ppm): 138.63, 138.24, IR (NaCl): 3600.9 w, 3542.1 w, 1537.1 s, 1484.2 m, 1413.7 m, 1372.5 s, 1325.5
60%
With sulfuric acid; urea; sodium nitrite; at 20 - 80℃; for 5h;
Add 24.0 mL (98%, 427.7 mmol, 26 eq. (excess)) sulfuric acid and 2.2 g (16.5 mmol,1.0 eq.) biimidazole to a round flask and agitate for 1 h. After dissolving the biimidazole, add 0.1 g (0.1 eq.) of urea as a catalystand then slowly add 8.3 g (97.7 mmol, 1.5 eq.) of sodium nitrate at 20-30 oC. The addition of sodium nitrate results in the production of dark brown NOx gas. After adding the sodium nitrate, allow the reaction to proceed for 5 h at 80 oC. Next, cool the reaction solution to 20 oC and slowly pour it into 1 L of ice water. Collect the precipitate product, 4,4'-5,5'-tetra-nitro-<strong>[492-98-8]2,2'-biimidazole</strong>, and wash it with cold water three times to remove the acid. This process gives 8.4 g of 4,4'-5,5'-tetranitro-<strong>[492-98-8]2,2'-biimidazole</strong> (yield:60%) We confirmed it by 1H-NMR, 13C-NMR and EA (element alanalysis).
Stage #1: 2,2'-biimidazole With sodium hydroxide In water; acetonitrile for 1h; Inert atmosphere;
Stage #2: ethyl iodide In water; acetonitrile for 6h; Inert atmosphere; Reflux;
With sodium hydroxide In water; N,N-dimethyl-formamide at 20℃; Inert atmosphere;
With hydrogenchloride; nickel(III) oxide; sodium hydroxide; In water; at 139.84℃; for 96h;pH 1.7;Autoclave;
An aqueous mixture (10.0 mL) containing H2biim (0.0500 mmol, 8.35 mg), Na2MoO4?2H2O (0.250 mmol, 60.4 mg), Ni2O3 (0.050 mmol, 8.35 mg), with a starting pH of 1.7 adjusted with 1.0 mol L-1 HCl and NaOH, was sealed in a 23.0 mL Parr Teflon-lined stainless steel auto-clave. Then it was heated to 413 K in an oven for 4 days, and finally cooled naturally to room temperate. Pale yellow block crystals were obtained in 25% yield (based on Mo). Anal. Calcd. (%) for C24H28Mo8N16O26 (Mr = 1724.14): C, 16.7; H, 1.62; N, 13.0. Found (%): C, 16.6; H, 1.61; N, 13.1. IR(KBr, cm-1) nu: 3157(s), 3036(m), 2941(s) 1650(s) 1560(s), 1500(m), 1419(m), 1317(s), 1215(s), 1114(s), 1098(s), 944(vs), 920(m), 881(vs), 840(s), 762(m), 722(m), 670(w).
1,2,4,5-tetrakis{2-(pyridin-4-yl)vinyl}benzene[ No CAS ]
[ 67-64-1 ]
[{(CO)3Re(μ2-2,2′-biimidazolate)2Re(CO)3}4(μ4-1,2,4,5-tetrakis(4-pyridylvinyl)benzene)2]*4(acetone)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
42%
In toluene; at 180℃; for 48.0h;Autoclave; High pressure;
A mixture of <strong>[14285-68-8]Re2(CO)10</strong> (100.9 mg, 0.1546 mmol) and Tkpvb (37.7 mg, 0.0768 mmol) and 2,2′-biimdazole (20.6 mg, 0.1535 mmol) in toluene-acetone (15 mL, v/v = 10:5) in a Teflon flask was placed in a steel bomb. The bomb was kept in an oven maintained at 180 C for 48 h and then cooled to 25 C. The golden yellow fine crystals were collected by filtration, washed several times with toluene and hexane, and air dried to give 2. Yield: 42% (63.1 mg). Anal. Calc. for C116H68N24O24Re8·4C3H6O: C, 39.38; H, 2.38; N, 8.61. Found: C, 39.41; H, 2.72; N, 8.22%. FT-IR (KBr): ν(CO) 2021 (s) 1896 (s) cm-1.
tetrakis(2-(2,4-fluorophenyl)pyrazolato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
Example 15: Synthesis of (tetrakis(2-(2,4-fluorophenyl)pyrazolato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(dfppz)2BIm]2) [0303] [0304] Under argon atmosphere, into a 100 mL Schlenk flask equipped with a stirrer were placed 234 mg (0.20 mmol) of di-mu-chloro-tetrakis(2-(2,4-fluorophenyl)pyrazolato) diiridium(III), 27 mg (0.20 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 40 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 16 hours. Subsequently, 55 mg (0.42 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 10 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with alumina (developing solvent: methylene chloride : 0.5 % triethylamine) for purification, to provide 155 mg of the desired compound as a pale yellow solid. (Yield: 63 %) The desired compound obtained was a mixture of isomers, and the product ratio was Isomer 1 (main product) : Isomer 2 = 60:40. [0305] Additionally, tetrakis(2-(2,4-fluorophenyl)pyrazolato)(mu-biimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0306] 1H-NMR (400MHz, C4D8O delta (ppm)) Isomer 1; 8.38 (d, 4H), 7.24 (d, 4H), 6.65-6.57 (m, 8H), 6.26 (s, 4H), 5.87 (dd, 4H) Isomer 2; 8.45 (d, 4H), 6.85 (d, 4H), 6.65-6.57 (m, 8H), 6.29 (s, 4H), 5.83 (dd, 4H) FD-MS (M/Z): 1232 M+
di-μ-chloro-tetrakis(3-methyl-1-(3,5-difluorophenyl)imidazoline-2-ylidene) diiridium (III)[ No CAS ]
bis(2',6'-difluoro-2,3'-bipyridinato)bis(3-methyl-1-(3,5-difluorophenyl)imidazoline-2-ylidene)(μ-bibenzimidazolyl)diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
43%
Example 22: Synthesis of (bis(2',6'-difluoro-2, 3'-bipyridinato)bis(3-methyl-1-(3,5-difluorophenyl)imidazoline-2-ylidene)(mu-bibenzimidazolyl) diiridium(III), Abbreviation; [Ir(dfpypy)(dfmpi)BBIm]2) [0330] [0331] Under argon atmosphere, into a 50 mL Schlenk flask equipped with a stirrer were placed 92 mg (0.08 mmol) of di-mu-chloro-tetrakis(2',6'-difluoro-2, 3'-bipyridinato) diiridium(III), 35 mg (0.15 mmol) of 2,2'-bibenzimidazole and 10 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 1 hour. Subsequently, 42 mg (0.32 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 16 hours. And then, 106 mg (0.08 mmol) of di-mu-chloro-tetrakis(3-methyl-1-(3,5-difluorophenyl)imidazoline-2-ylidene) diiridium(III) was added to the mixture, and the mixture was reacted under stirring at room temperature for 24 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with silica gel (developing solvent: methylene chloride) for purification, to provide 89 mg of the desired compound as a yellow solid. (Yield: 43 %) The desired compound obtained was a mixture of isomers, and the product ratio was Isomer 1 (main product) : Isomer 2 = 51:49. [0332] Additionally, bis(2',6'-difluoro-2, 3'-bipyridinato)bis(3-methyl-1-(3,5-difluorophenyl)imidazoline-2-ylidene)(mu-bibenzimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0333] 1H-NMR (400MHz, CD2Cl2, delta (ppm)) Isomer 1; 8.26-8.24 (m, 2H), 7.86-7.79 (m, 4H), 7.36 (d, 2H), 6.98-6.96 (m, 2H), 6.88-6.85 (m, 2H), 6.82-6.77 (m, 4H), 6.74-6.73 (m, 2H), 6.34-6.28 (m, 4H), 6.20-6.16 (m, 2H), 6.02-6.01 (m, 2H), 2.50 (s, 6H) Isomer 2; 8.26-8.24 (m, 2H), 8.02-8.00 (m, 2H), 7.83-7.79 (m, 2H), 7.29 (d, 2H), 7.00-6.97 (m, 2H), 6.88-6.85 (m, 2H), 6.82-6.77 (m, 4H), 6.74-6.73 (m, 2H), 6.34-6.28 (m, 4H), 6.20-6.16 (m, 2H), 5.98-5.97 (m, 2H), 3.04 (s, 6H) FD-MS (M/Z): 1384 M+
tetrakis(2-phenylpyridinato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
Example 16: Synthesis of (tetrakis(2-phenylpyridinato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(ppy)2BIm]2) [0307] [0308] Under argon atmosphere, into a 100 mL Schlenk flask equipped with a stirrer were placed 322 mg (0.30 mmol) of di-mu-chloro-tetrakis(2-phenylpyridinato) diiridium(III), 40 mg (0.30 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 60 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 13 hours. Subsequently, 83 mg (0.63 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 24 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with alumina (developing solvent: methylene chloride / hexane (volume ratio; 3/1) : 0.5 % triethylamine) for purification, to provide 113 mg of the desired compound as a yellow solid. (Yield: 33 %) The desired compound obtained was a mixture of isomers, and the product ratio was Isomer 1 (main product) : Isomer 2 = 61:39. [0309] Additionally, tetrakis(2-phenylpyridinato)(mu-biimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0310] 1H-NMR (400MHz, C4D8O, delta (ppm)) Isomer 1; 8.18 (dd, 4H), 7.86 (d, 4H), 7.70-7.55 (m, 8H), 6.81-6.72 (m, 8H), 6.66-6.62 (m, 4H), 6.38 (dd, 4H), 6.11 (s, 4H) Isomer 2; 7.92 (d, 4H), 7.78 (dd, 4H), 7.70-7.55 (m, 8H), 6.81-6.72 (m, 8H), 6.66-6.62 (m, 4H), 6.32 (dd, 4H), 6.13 (s, 4H) FD-MS (M/Z): 1132 M+
bis[2-(2,4-difluorophenyl)pyridinato-N,C6']iridium(III) chloride dimer[ No CAS ]
[ 492-98-8 ]
tetrakis(2-(2,4-difluorophenyl)pyridinato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
Example 4: Synthesis of (tetrakis(2-(2,4-difluorophenyl)pyridinato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(dfppy)2BIm]2) [0243] [0244] Under argon atmosphere, into a 250 mL Schlenk flask equipped with a stirrer were placed 486 mg (0.40 mmol) of di-mu-chloro-tetrakis(2-(2,4-difluorophenyl)pyridinato) diiridium(III), 54 mg (0.40 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 80 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 1 hour. Subsequently, 111 mg (0.84 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 2 hours. After the completion of the reaction, the reaction liquid was concentrated, and then methylene chloride, water and a saturated aqueous solution of ammonium chloride were added to the resultant concentrate until pH became 7, and the organic phase was separated from the water phase. The resultant organic phase was dried with sodium sulfate, and filtered, and then the filtrate was concentrated. And then, the resultant concentrate was washed with hexane, to provide 441 mg of binuclear iridium complex (1) as a yellow solid. (Isolation yield: 86 %) [0245] The obtained binuclear iridium complex (1) was a mixture of two different types of isomers, and the abundance ratio was 60:40. The binuclear iridium complex obtained as the main product (60 %) was referred to as "binuclear iridium complex (1a)" and the binuclear iridium complex obtained as the secondary product (40 %) was referred to as "binuclear iridium complex (1b)" [0246] Additionally, the binuclear iridium complex (1) was a novel compound, which had the following properties: [0247] 1H-NMR (400MHz, C4D8O, delta (ppm)); Binuclear iridium complex (1a); 8.17 (d, 4H), 8.13-8.12 (m, 4H), 7.79-7.75 (m, 4H), 7.91-7.15 (m, 4H), 6.49-6.42 (m, 4H), 6.22 (s, 4H), 5.84-5.81 (m, 4H) Binuclear iridium complex (1b); 8.24 (d, 4H), 7.85-7.81 (m, 4H), 7.74-7.72 (m, 4H), 6.95-6.91 (m, 4H), 6.49-6.42 (m, 4H), 6.24 (s, 4H), 5.77-5.74 (m, 4H) FD-MS (M/Z): 1276 (M+)
tetrakis(2',6'-difluoro-2,3'-bipyridinato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
28%
Example 13: Synthesis of (tetrakis(2',6'-difluoro-2, 3'-bipyridinato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(dfpypy)2BIm]2) [0297] [0298] Under argon atmosphere, into a 100 mL Schlenk flask equipped with a stirrer were placed 366 mg (0.30 mmol) of di-mu-chloro-tetrakis(2',6'-difluoro-2, 3'-bipyridinato) diiridium(III), 40 mg (0.30 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 60 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 3.5 hours. Subsequently, 83 mg (0.63 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 15 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with alumina (developing solvent: methylene chloride : 0.5 % triethylamine) for purification, to provide 110 mg of the desired compound as a pale yellow solid. (Isolation yield: 28 %) Additionally, tetrakis(2',6'-difluoro-2, 3'-bipyridinato)(mu-biimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0299] 1H-NMR (400MHz, CD2Cl2, delta (ppm)); 8.27 (dd, 4H), 7.89-7.84 (m, 4H), 7.67 (m, 4H), 6.89-6.93 (m, 4H), 6.33 (s, 4H), 5.78 (t, 4H) FD-MS (M/Z): 1280 M+
chloro(1-phenylpyrazole)iridium(III) dimer[ No CAS ]
[ 947589-85-7 ]
bis(1-phenylpyrazolato)bis(2',6'-difluoro-2,3'-bipyridinato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
13%
Example 18: Synthesis of (bis(1-phenylpyrazolato)bis(2',6'-difluoro-2, 3'-bipyridinato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(ppz)(dfpypy)BIm]2) [0315] [0316] Under argon atmosphere, into a 30 mL Schlenk flask equipped with a stirrer were placed 61 mg (0.05 mmol) of di-mu-chloro-tetrakis(2',6'-difluoro-2, 3'-bipyridinato) diiridium(III), 13 mg (0.10 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 10 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 3 hours. Subsequently, 28 mg (0.21 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 4 hours. And then, 51 mg (0.05 mmol) of di-mu-chloro-tetrakis(1-phenylpyrazolato) diiridium(III) was added to the mixture, and the mixture was reacted under stirring at room temperature for 14 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with alumina (developing solvent: methylene chloride / hexane (volume ratio; 2/1)) for purification, to provide 15 mg of the desired compound as a pale yellow solid. (Yield: 13 %) The desired compound obtained was a mixture of isomers, and the product ratio was Isomer 1 (main product) : Isomer 2 = 88:12. [0317] Additionally, bis(1-phenylpyrazolato)bis(2',6'-difluoro-2, 3'-bipyridinato)(mu-biimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0318] 1H-NMR (400MHz, CD2Cl2, delta (ppm)) Isomer 1; 8.24 (dd, 2H), 8.09 (dd, 2H), 7.86-7.82 (m, 2H), 7.74-7.72 (m, 2H), 7.23 (dd, 2H), 7.00-6.96 (m, 2H), 6.94-6.90 (m, 2H), 6.76 (dd, 2H), 6.74-6.70 (m, 2H), 6.47-6.46 (m, 2H), 6.37 (dd, 2H), 6.33 (d, 2H), 6.28 (d, 2H), 5.81 (m, 2H) Isomer 2; 8.19 (dd, 2H), 8.08 (m, 2H), 8.03 (dd, 2H), 7.80 (dd, 2H), 7.22-7.11 (m, 6H), 6.93-6.88 (m, 2H), 6.74-6.70 (m, 2H), 6.53-6.52 (m, 2H), 6.42 (dd, 2H), 6.32 (d, 2H), 6.28 (d, 2H), 5.85 (m, 2H) FD-MS (M/Z): 1184 M+
di-μ-chloro-tetrakis(3-methyl-1-phenylimidazoline-2-ylidene) diiridium(III)[ No CAS ]
tetrakis(3-methyl-1-phenylimidazoline-2-ylidene)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
Example 17: Synthesis of (tetrakis(3-methyl-1-phenylimidazoline-2-ylidene)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(mpi)2BIm]2) [0311] <strong>[492-98-8]2,2'-biimidazole</strong> and 2 ml of tetrahydrofuran. And then, the mixture was reacted under stirring at room temperature for 4 hours. Subsequently, 8.4 mg (0.21 mmol) of sodium hydride was added to the reaction mixture, and the mixture was further stirred for 19 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and the reaction mixture was concentrated until the solvent content became about 3 ml. Subsequently, 20 ml of diethyl ether was added to the resultant mixture. And then, the precipitate was collected by filtration, and dried under reduced pressure, to provide 92.6 mg of tetrakis(1-methyl-3-phenylimidazoline-2-ylidene)(mu-biimidazolyl) diiridium as a brownish white solid. (Yield: 81 %) The desired compound obtained was a mixture of isomers, and the product ratio was Isomer 1 (main product) : Isomer 2 = 53:43. [0313] Additionally, tetrakis(1-methyl-3-phenylimidazoline-2-ylidene)(mu-biimidazolyl) diiridium had the following properties: [0314] 1H-NMR (400MHz, CD2Cl2, delta (ppm)); Isomer 1: 7.45 (d, 4H), 7.04 (dd, 4H), 6.93 (d, 4H), 6.80 (dt, 4H), 6.62-6.44 (m, 8H), 6.15 (s, 4H), 3.03 (s, 12H) Isomer 2: 7.43 (d, 4H), 7.03 (dd, 4H), 6.91 (d, 4H), 6.79 (dt, 4H), 6.62-6.44 (m, 8H), 6.14 (s, 4H), 3.41 (s, 12H)
chloro(1-phenylpyrazole)iridium(III) dimer[ No CAS ]
tetrakis(1-phenylpyrazolato)(μ-biimidazolyl) diiridium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
Example 14: Synthesis of (tetrakis(1-phenylpyrazolato)(mu-biimidazolyl) diiridium(III), Abbreviation; [Ir(ppz)2BIm]2) [0300] [0301] Under argon atmosphere, into a 100 mL Schlenk flask equipped with a stirrer were placed 308 mg (0.30 mmol) of di-mu-chloro-tetrakis(1-phenylpyrazolato) diiridium(III), 40 mg (0.30 mmol) of <strong>[492-98-8]2,2'-biimidazole</strong> and 60 ml of tetrahydrofuran. And then, the mixture was stirred at room temperature for 7 hours. Subsequently, 83 mg (0.63 mmol) of tert-butoxy potassium (t-BuOK (85 wt% product)) was added to the mixture, and the mixture was reacted under stirring at room temperature for 16 hours. After the completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and then methylene chloride was added to the residue, and the insoluble substance was removed by filtration. The filtrate was concentrated under reduced pressure. The resultant crude reaction product was subjected to column chromatography with alumina (developing solvent: methylene chloride : 0.5 % triethylamine) for purification, to provide 180 mg of the desired compound as a pale ocher solid. (Isolation yield: 55 %) Additionally, tetrakis(1-phenylpyrazolato)(mu-biimidazolyl) diiridium(III) was a novel compound, which had the following properties: [0302] 1H-NMR (400MHz, CD2Cl2, delta (ppm)); 8.35 (dd, 4H), 7.29 (dd, 4H), 6.76-6.80 (m, 8H), 6.61-6.56 (m, 4H), 6.50-6.48 (m, 4H), 6.39-6.39 (dd, 4H), 6.18 (s, 4H) FD-MS (M/Z): 1088 M+
[Cu(biim)(acac)(H2O)]2[Cu(acac)2(ClO4)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
A methanol solution (10 mL) of Cu(ClO4)2·6H2O (0.33 g, 2 mmol) was initially reacted with acetylacetone (0.02 g, 2 mmol) treated with NaOH (0.040 g, 1.0 mmol) in water (10 mL) under magnetic stirring at room temperature. After 30 min, a 20 mL methanolic solution of the biimidazole (0.15 g, 2 mmol) was added to the solution and the resulting mixture was stirred for 2 h at room temperature. The green colored solid was isolated and washed with cold aqueous methanol and finally dried over P4O10 (Yield: 67%).
[Zn(5-bromonicotinate)2(2,2'-biimidazole)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
With sodium hydroxide; In water; at 160℃; for 72h;Autoclave;
A mixture of Zn(NO3)2 6H2O (44.6mg,0.15mmol),5-Brnic(60.6 mg,0.3mmol),H2biim (20.1mg,0.15mmol),NaOH(12.0mg,0.3 mmol),and H2O (10mL)was stirred at room temperature for 15min,and then sealed in a25mL Teflon-lined stainless steel vessel,and heated at 160 1C for 3days,followed by cooling to room temperature at a rate of 10 1C/h. Colorless block-shaped crystals were isolated manually,and washed with distilled water.Yield: 55%(basedon5-BrnicH).CalcdforC24H14Br2ZnN4O4:C 44.51%,H2.18%,N8.65%.Found:C44.17%,H1.84%,N8.24%.IR (KBr,cm1): 1609vs,1552m,1441m,1394w,1370vs,1342w,1281m,1237w,1181w,1125s,1088w,1028m,991w,925w,887w,862w,771m,754m,732m,687m,553w,and434w.
2,2'-Biimidazole (0.27 g, 2 mmol) and NaOH (0.32 g, 8 mmol) were placed in a 100 mL round bottomed flask with 20 mL of acetonitrile. The mixture was stirred at room temperature for two hours. 3-Picolyl chloride hydrochloride (0.65 g, 4 mmol) in acetonitrile (20 mL) was added to the mixture and refluxed for 24 h at 50-60 C. The reaction was monitored with TLC and upon completion the solvent was removed by rotary evaporation. The residue was dissolved in water (50 mL) and extracted with methylene chloride (30 mL * 3). Organic layers were combined, dried over anhydrous MgSO4 and rotary evaporated to obtain the brown color powder as the product. Yield: 0.45 g (71%); mp 112-115 C; 1H NMR (deltaH; CDCl3, 400 MHz):8.46 (d, 2H), 8.45 (s, 2H), 7.39 (d, 2H), 7.17 (m, 2H), 7.11 (d, 2H), 6.95 (d, 2H), 5.78 (s, 4H).
2,2'-Biimidazole (0.27 g, 2 mmol) and NaOH (0.32 g, 8 mmol) were placed in a 100 mL round bottomed flask with 20 mL of acetonitrile. The mixture was stirred at room temperature for two hours. 2-Picolyl chloride hydrochloride (0.65 g, 4 mmol) in acetonitrile (20 mL) was added to the mixture and refluxed for 24 h at 50-60 C. The reaction was monitored with TLC and upon completion the solvent was removed by rotary evaporation. The residue was dissolved in water (50 mL) and extracted with methylene chloride (30 mL * 3). Organic layers were combined, dried over anhydrous MgSO4 and rotary evaporated to obtain the pale brown color powder as the product. Yield: 0.25 g (40%); mp 180-183 C; 1H NMR (deltaH; CDCl3, 400 MHz): 8.53 (d, 2H), 7.53 (t, 2H), 7.15 (t, 2H), 7.12 (s, 2H), 7.07 (s, 2H), 7.05 (d, 2H), 5.87 (s, 4H).
2,2'-Biimidazole (0.33 g, 2.48 mmol) and NaOH (0.39 g, 9.92 mmol) were placed in a 100 mL round bottomed flask with 20 mL of acetonitrile. The mixture was stirred at room temperature for two hours. Benzyl bromide (0.63 g, 5 mmol) in acetonitrile (20 mL) was added to the mixture and refluxed for 24 h at 50-60 C. The reaction was monitored with TLC and after completion the solvent was removed by rotary evaporation. The residue was dissolved in water (50 mL) and extracted with methylene chloride (30 mL * 3). Organic layers were combined, dried over anhydrous MgSO4 and rotary evaporated to obtain the yellow color powder as the product. Yield: 0.69 g (89%); mp 144-146 C; 1H NMR (deltaH; CDCl3, 400 MHz):5.70 (s, 4H), 6.93 (d, 2H), 7.03 (m, 4H), 7.12 (d, 2H), 7.24 (m, 6H).
<strong>[492-98-8]2,2'-biimidazole</strong> (0.27 g, 2 mmol) and NaOH (0.32 g, 8 mmol) were placed in a 100 mL round bottomed flask with 20 mL of acetonitrile.The mixture was stirred at room temperature for two hours. 4-picolyl chloride hydrochloride (0.65 g, 4 mmol) in acetonitrile (20 mL) was added to the mixture and refluxed for 24 h at 50-60 C. The reaction was monitored with TLC and after completion the solvent was removed by rotary evaporation. The residue was dissolved in water (50 mL) and extracted with methylene chloride (30 mL * 3). Organic layers were combined, dried over anhydrous MgSO4 and rotary evaporated to obtain the dark brown color powder as the product. Yield: 0.35 g (56%); mp 157-160 C; 1H NMR (deltaH; CDCl3, 400 MHz):8.49 (d, 4H), 7.11 (d, 2H), 6.94 (d, 2H), 6.91 (d, 4H), 5.84 (s, 4H).
With hydrogenchloride; In water; at 150℃; for 48h;pH 2.5;Autoclave; High pressure;
A mixture of Na2MoO4*2H2O (0.0718 g, 0.296 mmol), <strong>[492-98-8]2,2'-biimidazole</strong> (biim, 0.0430 g, 0.257 mmol), NiF2*4H2O (0.0095 g, 0.056 mmol), and Na2SiO3*9H2O (0.0708 g, 0.249 mmol) in H2O (10 mL) was adjusted to pH 2.5 with HCl (1.0 mol/L solution in water) and heated at 150 C for 48 h in a sealed 25 mL teflon-lined stainless vessels under autogenous pressure. After cooling to ambient temperature with 800 min, black block crystals (yield50%, based on Na2MoO4*2H2O) were obtained.
With sodium hydroxide; In water; at 150℃; for 72h;pH 5.0;Autoclave; High pressure;
A mixture of Zn(NO3)2·6H2O (0.1mmol, 30mg), H2biim (0.1mmol, 13mg), H2pzdc (0.1mmol, 20mg) and H2O (8mL) was adjusted to pH 5.0 with 0.05 mol L-1 NaOH solution. It was then sealed in a 25mL Teflon reactor and heated at 150 C for 72 h. Finally the mixture was cooled to room temperature at a cooling rate of 3 C h-1 and block colorless crystals of 1 were obtained by filtration. 1 was washed with distilled water and dried in air. Yield: 47% based on the Zn(II) salt. Anal. Calc. for C12H8N6O4Zn: C, 39.42; H, 2.21; N, 22.99. Found: C, 39.40; H, 2.20; N, 22.91%. IR (KBr, cm-1): 3088 (w), 2993 (w), 2897 (w), 2777 (s), 1608 (s), 1564 (s), 1536 (s), 1457 (s), 1442 (s), 1359 (m), 1322 (m), 1231 (m), 1204 (s), 1170 (s), 1121 (m), 1107 (m), 1064 (s), 993 (s), 946 (m), 859 (s), 833 (m), 772 (m), 740 (s), 693 (s), 665 (s).
With sodium hydroxide; In water; at 150℃; for 72h;pH 5.0;Autoclave; High pressure;
General procedure: A mixture of Zn(NO3)2·6H2O (0.1mmol, 30mg), H2biim (0.1mmol, 13mg), H2pzdc (0.1mmol, 20mg) and H2O (8mL) was adjusted to pH 5.0 with 0.05 mol L-1 NaOH solution. It was then sealed in a 25mL Teflon reactor and heated at 150 C for 72 h. Finally the mixture was cooled to room temperature at a cooling rate of 3C h-1 and block colorless crystals of 1 were obtained by filtration. 1 was washed with distilled water and dried in air. Yield: 47% based on the Zn(II) salt.
With sodium hydroxide; In water; at 150℃; for 72h;pH 5.0;Autoclave; High pressure;
A mixture of CdCl2·2.5H2O (0.1mmol, 30mg), H2biim (0.1mmol, 10mg) and H2ip-OH (0.1mmol, 20mg) and H2O (8mL) was adjusted to pH 5.0 with 0.05 mol L-1 NaOH solution. It was then sealed in a 25mL Teflon reactor and heated at 150 C for 72 h. The mixture was cooled to room temperature after 40 h. Slightly purple crystals were obtained. Yield: 42 % based on the Cd(II) salt. Anal. Calc. for C11H7N2O5Cd: C, 36.70; H, 1.95; N, 7.79. Found: C, 36.76; H, 1.95; N, 7.80%. IR (KBr, cm-1): 3461 (m), 3058 (w), 2930 (w), 2866 (w), 1630 (s), 1583 (s), 1508 (m), 1397 (s), 1333 (s), 1291 (s), 1208 (m), 1165 (w), 1098 (w), 1014 (w), 859 (s), 750 (s), 661 (m), 428 (w).
1,1′:2′,1″-terphenyl-3,3″,4′,5′-tetracarboxylic acid[ No CAS ]
[Zn2(ttac)(dimidazole)H2O]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57.9%
With potassium hydroxide; In water; at 140℃; for 72h;pH 6;Autoclave;
A mixture of 4,5-di- (3'-carboxylphenyl)-phthalic acid (0.05 mmol, 20.3 mg), zinc perchlorate-hydrate (0.1 mmol, 26.4 mg) and dimidazole (0.1 mmol, 13.4 mg) in 10 mL of water was adjusted to pH 6.0 with 1mol L-1 KOH solution. The mixture was then transferred to and sealed in a 25mL Teflon-lined stainless autoclave, followed by heating at 140 C for 72 h to afford colorless block-shaped crystals in 57.9% yield after slowly cooling to room temperature at a rate of 5 C/h. Elemental analysis calculated for C28H16Zn2N4O9 (683.19): C 50.47%, H 3.52%, N 8.59%; Found: C 49.22%, H 3.36%, N 8.20%. Selected IR (cm-1): 3284(m), 3143(m), 2937(m), 1554(s), 1398(s), 1357(m), 1266(w), 1179(w), 1098(m), 1001(w), 910(w), 813(m), 769(s), 698(m), 654(w), 586(w), 555(w), 499(w), 448(w).
{Ag5(2,2'-biimidazole)2(Hbiim-NO2)2[PW12O40][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With nitric acid; In water; at 160℃; for 120h;pH 2;Autoclave; High pressure;
Compound 2 was synthesized hydrothermally by reaction of H3PW12O40 xH2O (0.075g, 0.026 mmol), AgNO3 (0.051g, 0.3 mmol), H2biim (0.008g, 0.06 mmol) and 10 mL distilled water in a 25 ml Teflon-lined autoclave. The pH was adjusted to 2 with 1.0 mol L-1 HNO3. The mixture was heated under autogenous pressure at 160 C for 5 days and then was left to cool to room temperature. Red crystals could be isolated in about 60% yield and dried at room temperature for the further characterization. Anal.Calcd for 2: C7.13,H0.50, N6.23. Found: C7.02,H0.45,N6.42%. IR(ITR mode,cm1): 1502(s),1412(w),1352(s),1243(w),1153(s),1075(s),968(s),890(s),793(s).The IR spectrum of compound 2 is shown in the Supporting information (Fig. S6).
With potassium hydroxide; In water; for 8h;Reflux;
General procedure: 2,2'-Biimidazole (0.4 g, 3 mmol) was added to a 100mLthree-necked flask charged with 3-chloropropionic acid (1.3 g,12 mmol), KOH (0.336 g, 6 mmol), and water (10 mL) at roomtemperature. The reaction mixture was adjusted to a pH level of10 to 12 with a 5M aqueous solution of KOH and the reactionmixture was heated slowly to reflux for 8 h. The product mixturewas acidified to pH2-3 with hydrochloric acid (1 M), and thenconcentrated under reduced pressure. The concentrated mixturewas diluted with ethanol and filtered to remove the undissolvedsalt. The final filtrate was concentrated to give a brown viscousliquid (85.1% yield). The product was dried overnight undervacuum before use and analysis. dH (D2O) 2.51 (t, J 6.0, 8H),3.74 (t, J 6.0, 8H), 7.40 (s, 4H). m/z (ESI-MS, ve mode)423.1565 [MH]; calcd for C18H24N4O8 2, 424.1589.
With potassium hydroxide; In water; for 8h;Reflux;
General procedure: 2,2'-Biimidazole (0.4 g, 3 mmol) was added to a 100mLthree-necked flask charged with 3-chloropropionic acid (1.3 g,12 mmol), KOH (0.336 g, 6 mmol), and water (10 mL) at roomtemperature. The reaction mixture was adjusted to a pH level of10 to 12 with a 5M aqueous solution of KOH and the reactionmixture was heated slowly to reflux for 8 h. The product mixturewas acidified to pH2-3 with hydrochloric acid (1 M), and thenconcentrated under reduced pressure. The concentrated mixturewas diluted with ethanol and filtered to remove the undissolvedsalt. The final filtrate was concentrated to give a brown viscousliquid (85.1% yield). The product was dried overnight undervacuum before use and analysis.
[bis(2-(N-carbazolyl)pyridinato-N,C(3'))Ir(μ-Cl)]2[ No CAS ]
[(9-(pyridine-2-yl)-9H-carbazole)2Ir(1H,1'H-2,2'-biimidazole)Cl][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
0.18 g
With sodium carbonate; In 2-ethoxy-ethanol; at 100℃; for 16h;Inert atmosphere;
The ligand [67] (cpy) (0.40 g, 1.6 mmol), IrCl3H2O (0.2 g,0.67 mmol) in a mixed solvent of 2-ethoxyethanol (10 mL) and water (3 mL) was stirred under nitrogen at 120 C for 24 h. Cooled to room temperature, the precipitate was collected by filtration and washed with water, ethanol and hexane successively and then dried in vacuum to give a cyclometalated Ir(III) m-chloro-bridged dimer. The dimer (0.2 g, 0.17 mmol), biim (0.0771 g, 0.58 mmol) and Na2CO3 (0.18 g, 1.75 mmol) were dissolved in 2-ethoxyethanol (10 mL) and the mixture was then stirred under argon at 100 C for16 h. After cooling to room temperature, the precipitate was filtered off and washed with water, ethanol and hexane. The crude product was chromatographed on silica gel using CH2Cl2 as eluent to afford the desired Ir(III) complex [(cpy)2Ir(biim)Cl] as green solid. Yield: 35%. (0.18 g). M.p. 280 C (dec). Anal. Calc. (%) for C40-H28IrN8Cl: C, 56.62, H, 3.33, N, 13.21. Found (%): C, 56.36, H, 3.47, N,12.98. FT-IR (KBr, m, cm1 selected peaks: 3100 s, 3037 s, 1608 s,1175 s, 762 s (br, broad; s, sharp). UV-Vis in DCM [kmax/nm(emax/-mol1 cm1)]: 253(1077), 290(754), 345(300), 466(87), 485(11).1H NMR (300 MHz, CDCl3) d (ppm): 6.15(d, J = 7.2 Hz, 1H), 6.35(t, J = 6.5 Hz, 1H), 6.42 (m. 1H), 6.92 (m, 2H), 7.22 (m, 4H), 7.42(m, 5H), 7.61 (m, 5H), 7.85 (m, 5H), 7.92 (m, 2H), 8.15 (m, 2H).13C NMR (75.46 MHz; CDCl3) d (ppm): 76.60, 77.22, 113.31,115.38, 118.78, 119.25, 121.18, 123.34, 124.01, 126.07, 125.49,126.40, 129.88, 136.08, 138.49, 144.24, 151.62, 156.18 and173.56. ESI-MS (CH3OH) m/z (%): 848 [M+], 813(75) [M+Cl], 680(10) [M+Cl, biim]. Conductivity (KM/S cm2 mol1) in DMF: 55.The complexes [(cpy)2Ir(bpy)Cl] (2) and [(cpy)2Ir(dppe)Cl] (3) were synthesized by following the above procedure using 2,2-bipyridine (0.09 g, 0.58 mmol) and 1,2-bis (diphenylphosphino)ethane (0.23 g, 0.58 mmol), respectively, instead of using biimidazole.
[Cu(2,2′-biimidazole)]2(triethylamine)2[HPW12O40]·H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62.5%
A mixture of 14 Na2WO4 (0.329g, 1.00mmol), 15 H3PO4 (0.147g, 1.50mmol), 16 H2C2O4 (0.270g, 1.00mmol), 17 Cu(CH3OO)2 (0.356g, 1.50mmol), biim (0.067g, 0.50mmol), 18 TEA (0.03g, 0.50mmol) and 19 H2O (20ml) were stirred for 30min, then 20 NH3·H2O was added to adjust the pH value to 6.5. Finally, the suspension was transferred to a 30ml Teflon-lined autoclave and heated at 160C for 120h under autogenous pressure. After the system was cooled to room temperature, black block crystals were filtered and dried at room temperature. Yield: 62.5% (based on W). Anal. Calcd. for C48H90Cu4N20O82P2W24: C, 8.25; H, 1.30; N, 4.01; W, 63.13; Cu, 3.64; P, 0.89. Found: C, 8.28; H, 1.25; N, 4.06; W, 63.02; Cu, 3.73; P, 0.87. IR (cm-1): 3447, 3302, 1642, 1566, 1514, 1414, 1090, 1063, 965, 879, 818, 785, 677
[Cu(2-hydroxynaphthaldehyde)(2,2'-bi-1H-imidazole)ClO<SUB>4</SUB>][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
66%
In ethanol; at 20℃; for 4h;
General procedure: To an ethanolic solution of copper perchlorate hexahydrate (0.74?g, 2.00?mM), 5-nitrosalicylaldehyde (0.28?g, 2.00?mM) and 2,2'-bipyridyl (0.35?g, 2.00?mM) in ethanol (10?mL) were added consequently with continuous stirring at room temperature for 4?h. The removal of solvent from the resultant dark green solution obtained green precipitate was washed with water, ethanol, ether, and dried under vacuum. The obtained precipitate was recrystallized in acetonitrile solvent by slow evaporation giving X-ray quality single crystals after a few days. Yield: 1.00?g (75%); m.p.: 284?C. Anal. data for C17H12ClCuN3O8 Calc. (%): C, 42.07; H, 2.49; N, 8.66; Cu, 13.09; Found (%): C, 42.12; H, 2.40; N, 8.58; Cu, 13.02; IR (nu, cm-1) (KBr Disc): 1633(nu C=0); 1609(nu C=N); 1573 (nu C-O); 622(nu Cu-O); lambdamax, nm (epsilon, M-1?cm-1) in DMF: : 624(198), 532 (984), 430 (144758), 372 (104638), 312 (100213), 264 (85070); Molar conductivity (Lambdam/S?cm2?mol-1) in CH3CN 17. g??=?2.06, g||?=?2.25 and A||?=?326. Other copper(II) complexes 2-4 were synthesized by a procedure similar to the synthesis of complex 1.
[Cu(5-nitrosalicylaldehyde)(2,2'-bi-1H-imidazole)(ClO<SUB>4</SUB>)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
In ethanol; at 20℃; for 4h;
General procedure: To an ethanolic solution of copper perchlorate hexahydrate (0.74?g, 2.00?mM), 5-nitrosalicylaldehyde (0.28?g, 2.00?mM) and 2,2'-bipyridyl (0.35?g, 2.00?mM) in ethanol (10?mL) were added consequently with continuous stirring at room temperature for 4?h. The removal of solvent from the resultant dark green solution obtained green precipitate was washed with water, ethanol, ether, and dried under vacuum. The obtained precipitate was recrystallized in acetonitrile solvent by slow evaporation giving X-ray quality single crystals after a few days. Yield: 1.00?g (75%); m.p.: 284?C. Anal. data for C17H12ClCuN3O8 Calc. (%): C, 42.07; H, 2.49; N, 8.66; Cu, 13.09; Found (%): C, 42.12; H, 2.40; N, 8.58; Cu, 13.02; IR (nu, cm-1) (KBr Disc): 1633(nu C=0); 1609(nu C=N); 1573 (nu C-O); 622(nu Cu-O); lambdamax, nm (epsilon, M-1?cm-1) in DMF: : 624(198), 532 (984), 430 (144758), 372 (104638), 312 (100213), 264 (85070); Molar conductivity (Lambdam/S?cm2?mol-1) in CH3CN 17. g??=?2.06, g||?=?2.25 and A||?=?326. Other copper(II) complexes 2-4 were synthesized by a procedure similar to the synthesis of complex 1.
A mixture of H2ATIBDC (0.084 g, 0.150 mmol) and NaOH (0.3 ml, 0.5 mol/l) was dissolved in water (5 ml) and then an aqueous solution of CdCl2·2.5H2O (0.034 g, 0.150 mmol) in water (5 ml) was added whilst stirring. To this solution biim (0.008 g, 0.050 mmol) in methanol (5 ml) was added and then filtered. The compound was obtained from the filtrate with a 68% yield based on H2ATIBDC. Anal. Calc. for C14H12CdI3N5O6: C, 22.09; H, 1.59; N, 9.20. Found: C, 22.20; H, 1.50; N, 9.28%.
General procedure: A mixture of H2ATIBDC (0.084 g, 0.150 mmol) and NaOH (0.3 ml, 0.5 mol/l) was dissolved in water (5 ml) and then an aqueous solution of CdCl2·2.5H2O (0.034 g, 0.150 mmol) in water (5 ml) was added whilst stirring. To this solution biim (0.008 g, 0.050 mmol) in methanol (5 ml) was added and then filtered. The compound was obtained from the filtrate with a 68% yield based on H2ATIBDC.
dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer[ No CAS ]
[(η5-Cp)RhCl(2,2′-biimidazole)]PF6[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
In methanol; dichloromethane; at 65℃; for 10h;
A mixture of the precursor compound [CpRh(mu-Cl)Cl]2(0.1 mmol, 0.0618 g) in 5 ml of methanol was added dropwiseto a 15 ml mixed solution of the ligand 2,2?-biimidazole(CH3OH:CH2Cl2; 3 V:1 V) (0.2 mmol, 0.026 g) and NH4PF6(0.25 mmol, 0.0407 g). The reaction mixture was stirred andrefluxed for 10 h. After that step, the solution was allowed tostand at room temperature to crystallize. The resulting complexwas filtered off and dried in a vacuum box after a week.The crystals were collected at 62% yield. Anal. Calc. (%) forC16H21ClF6N4PRh:C, 34.77; H, 3.83; N, 10.13. Found: C,34.20; H, 3.51; N, 9.64; 1H NMR (600 MHz, DMSO-d6, deltappm): 1.68 [15H, (Cp-C11-15H3)]; 7.56 (2H, s, C4/4?H); 7.54(2H, s, C5/5?H); 12.90 (2H, s, N1/1?H). 13C NMR (150 MHz,DMSO-d6, delta ppm): 9.3 (Cp-C11-15H3); 95.4 (Cp-C6-10)(J = 8.2 Hz); 138.2 [C2/2?(H2biim)]; 128.2 [C4/4?(H2biim)];121.4 [C5/5?(H2biim)]. 15N NMR (43.5 MHz, DMSO-d6, deltappm): - 218.7 (N1/1?H); - 173.8 (N3/3?) (J = 18.6 Hz). IR(cm-1): 3169(w), 1531(ms), 1433(ms), 1179(ms), 1095(ms),1021(ms), 836(vs), 746(ms), 608(ms), 557(s).
In water; at 159.84℃; for 144h;Sealed tube; Autoclave;
A mixture of CuCl22H2O (0.068 g, 0.40 mmol), K3[Fe(CN)6](0.099 g, 0.30 mmol) and 2,20-biimidazole (0.101 g, 0.75 mmol)in H2O (7 ml) was stirred for 15 min at room temperature,then sealed in a 15 ml Teflon-lined stainless steel containerand heated to 433 K for 6 d. After it had been cooled to roomtemperature at a rate of 10 K h1, red block-shaped crystalswere obtained in 40% yield (based on Cu). Analysis calculated(%) for C4H3CuN3, (I): C 30.67, H 1.93, N 26.82; found: C 30.46, H 1.85, N 26.95. IR (KBr, pellet, cm1): (N-H) 3448(w), (C-H) 3318 (w), (C N) 2108, 2042 (s), (C C andC N) 1526 (m).
Under the protection of nitrogen, add sodium hydride (0.048g, 1.20mmol) and 8mL of N,N-dimethylformamide to a 50mL Schlenck bottle. At 0C, add biimidazole compound 1a (0.060g, 0.45 mmol) and stir at low temperature 30 minutes later,Add chiral compound 2a (0.296g, 0.50mmol). After addition, warm up to room temperature and perform TLC monitoring. After about 2 hours of reaction, the reaction substrate remains. After extending the reaction time for 12 hours, the reaction of compound 2a is complete and the reaction is stopped. , Post-processing. Quench with water, add ethyl acetate to separate the liquid, extract with ethyl acetate (20mL×3), obtain the organic phase, dry with anhydrous sodium sulfate, wash with water (30mL×2), remove the solvent under reduced pressure, and column chromatography to obtain compound 3aa White solid 0.142g, yield 56%.
Under the protection of nitrogen, add 10mL of sodium hydride (0.090g, 2.25mmol) and N,N-dimethylformamide to a 50mL Schlenck bottle. At 0C, add the biimidazole compound 1a (0.111g, 0.83 mmol) and stir at low temperature After 30 minutes, chiral compound 2b (0.519g, 0.75mmol) was added. After the addition was completed, the temperature was raised to room temperature and the reaction was monitored by TLC. After 2 hours of reaction, the reaction substrate remained. After prolonging the reaction time for 12 hours, compound 2b reacted Complete, stop the reaction, and work up. Quench with water, add ethyl acetate to separate the layers, extract with ethyl acetate (20mL×3), obtain the organic phase, dry with anhydrous sodium sulfate, wash with water (30mL×2), remove the solvent under reduced pressure, and column chromatography to obtain compound 3ba White solid 0.201g, yield 40%.
Under the protection of nitrogen, add 5mL of sodium hydride (0.024g, 0.60mmol) and N,N-dimethylformamide to a 50mL Schlenck bottle. At 0C, add the biimidazole compound 1a (0.030g, 0.22 mmol) and stir at low temperature After 30 minutes, add chiral compound 2c (0.126g, 0.20mmol). After addition, warm up to room temperature to react. TLC monitoring, reaction for about 2 hours, the reaction substrate remains, after extended reaction time for 12 hours, compound 2c react Complete, stop the reaction, and work up. Quench with water, add ethyl acetate to separate the liquid, extract with ethyl acetate (20mL×3), obtain the organic phase, dry with anhydrous sodium sulfate, wash with water (30mL×2), remove the solvent under reduced pressure, and column chromatography to obtain compound 3ca White solid 0.069g, yield 58%.
Under the protection of nitrogen, add 5mL of sodium hydride (0.024g, 0.60mmol) and N,N-dimethylformamide to a 50mL Schlenck bottle. At 0C, add the biimidazole compound 1a (0.030g, 0.22 mmol) and stir at low temperature After 30 minutes, add chiral compound 2d (0.179g, 0.20mmol). After addition, warm to room temperature to react. TLC monitoring. The reaction takes about 2 hours. The reaction substrate is left. After prolonging the reaction time for 12 hours, compound 2d reacts Complete, stop the reaction, and work up. Quench with water, add ethyl acetate to separate the layers, extract with ethyl acetate (20mL×3), obtain the organic phase, dry with anhydrous sodium sulfate, wash with water (30mL×2), remove the solvent under reduced pressure, and obtain the compound 3da White solid 0.076g, yield 44%.
Under the protection of nitrogen, add 5mL of sodium hydride (0.024g, 0.60mmol) and N,N-dimethylformamide to a 50mL Schlenck bottle. At 0C, add the biimidazole compound 1a (0.030g, 0.22 mmol) and stir at low temperature After 30 minutes, chiral compound 2e (0.140g, 0.20mmol) was added. After the addition, the temperature was raised to room temperature and the reaction was monitored by TLC. After 2 hours of reaction, the reaction substrate remained. After extending the reaction time for 12 hours, compound 2e reacted Complete, stop the reaction, and work up. Quench with water, add ethyl acetate to separate the layers, extract with ethyl acetate (20mL×3), obtain the organic phase, dry with anhydrous sodium sulfate, wash with water (30mL×2), remove the solvent under reduced pressure, and column chromatography to obtain compound 3ea White solid 0.084g, yield 62%.
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