* 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: for 24 h; Inert atmosphere; Reflux Stage #2: With manganese(IV) oxide In tolueneInert atmosphere; Reflux
Under nitrogen 18.6g (0.31 mmol) of 1,2-diaminoethane was added 1000ml of toluene 55.0g (0.26 mol) of 9,10-dioxo Philippines.Use trap the red suspension is heated under reflux for 24 hours (separation of water: approximately 1ml).The resulting brownish suspension is treated with 50.0g of manganese oxide (IV), and heating continued under reflux until no intermediate product is visible on TLC.The hot black suspension was filtered by washing with 200ml of toluene and the solid residue.The solution was concentrated and the resulting solid was further dried in vacuo to give a pale yellow solid as the title compound (Yield: 58.0g (97percent)).
Reference：
[1] Patent: CN101970448, 2016, B, . Location in patent: Paragraph 0381; 0382
[2] Recueil des Travaux Chimiques des Pays-Bas-Journal of the Royal Netherlands, 1996, vol. 115, # 5, p. 275 - 285
[3] Chemische Berichte, 1886, vol. 19, p. 112[4] Chemische Berichte, 1887, vol. 20, p. 268
[5] Journal of the Chemical Society, 1889, vol. 55, p. 98[6] Journal of the Chemical Society, 1893, vol. 63, p. 1286
[7] Russian Journal of General Chemistry, 2006, vol. 76, # 6, p. 843 - 848
2
[ 107-15-3 ]
[ 84-11-7 ]
[ 217-68-5 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas-Journal of the Royal Netherlands, 1996, vol. 115, # 5, p. 275 - 285
3
[ 84-11-7 ]
[ 53348-05-3 ]
Yield
Reaction Conditions
Operation in experiment
90%
With bromine; dibenzoyl peroxide In nitrobenzene at 60℃; for 17 h; Irradiation
A mixture of phenanthrenequinone (5.0 g, 24 mmol), Br2 (2.6 mL, 50.4 mmol), nitrobenzene (45 mL), and benzoyl peroxide (0.25 g, 1 mmol) was exposed to a tungsten lamp and heated at 60 °C for 17 h. The reaction mixture was allowed to cool down to room temperature. The light brown crystals were collected by filtration and washed with ethanol. A second of the crop of crystals were obtained after cooling in ice. The crystals were dried under vacuum at 60 °C overnight to give light brown crystals (7.84 g, 90percent). The product was recrystallized from nitrobenzene to give orange brown crystals. 1H NMR (300 MHz, CDCl3, δ): 8.10 (d, J= 2.0 Hz, 2H), 8.05 (d, J= 8.3 Hz, 2H), 7.65 (dd, J= 8.3 Hz, 2.0 Hz, 2H). 13C{1H} NMR (75 MHz, CDCl3, δ): 178.87, 135.97, 133.43, 132.08, 129.92, 127.40. HRMS-FAB (m/z): [M + H]+ calcd for C14H7O2Br2, 364.8813; found, 364.8813. Anal. Calcd for C14H6Br2O2: C, 45.94; H, 1.64; Br, 43.66. Found: C, 45.95; H, 1.57; Br, 43.71.
82%
With bromine; dibenzoyl peroxide In nitrobenzeneReflux
20.50 g of phenanthrenequinone, 48 g of bromine,1.0 g of benzoyl peroxide and 300 ml of nitrobenzene,Add reflux for 2-3 hours,Cool down to room temperature,filter,The solid was washed with 400 ml of ethanol and dried to give 29.21 g of TM-1.The yield was 82percent.
80%
With bromine; dibenzoyl peroxide In nitrobenzene at 140℃; for 8 h;
In a 250 mL three-necked flask,Followed by adding 5.2 g of phenanthrenequinone, 0.4 g of benzoyl peroxide,Liquid bromine 1.5g and solvent nitrobenzene 160mL, raised to 140 , the reaction to the hydrogen bromide gas generated after the continued drop of liquid bromine 16g. After 8 h, the reaction was cooled toThe filter cake was washed with absolute ethanol and several times until the filtrate was colorless and 7.32 g (80percent) of the desired solid product was obtained.
80%
With bromine; dibenzoyl peroxide In nitrobenzene at 120℃; for 1.5 h; Inert atmosphere
9,10-phenanthrenequinone (10.006 g, 48.02 mmol) was dissolved 60 mL of nitrobenzene, Under nitrogen protection, Add benzoyl peroxide (0.980 g, 4.05 mmol), Add 1mLBr2, Heated to 120 ° C, Produce a large amount of HBr gas, And then slowly dropping 4 mL of Br2, After the dropwise addition, the mixture was stirred at 120 ° C for 1.5 h, Cooled to room temperature, Adding a small amount of saturated NaHSO3 solution, Then add 60mL petroleum ether, a large number of yellow solid appears, filter, Wash the filter cake with a large amount of petroleum ether, A yellow solid (11.20 g, 80percent) was obtained.
70%
With bromine; dibenzoyl peroxide In ethanol; nitrobenzene
EXAMPLE 5 Synthesis of 7,10-bis{3-(diphenylamino)carbazol-9-yl}-1,4-diazatriphenylene (Compound 31) 9,10-Phenanthrenequinone (50 g), benzoyl peroxide (2.5 g), and nitrobenzene (250 mL) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen. Bromine (83 g) was added, and the mixture was heated and stirred for 2 hours under reflux. After left to cool, ethanol (250 mL) was added, and a precipitated solid was collected by filtration. The solid was washed with ethanol and subjected to vacuum drying to obtain a yellow solid of 3,6-dibromo-9,10-phenanthrenequinone (yield 70percent).
63%
With aluminum (III) chloride; bromine In nitrobenzene at 105℃; for 3.66 h; Inert atmosphere
Under nitrogen protection,To 230 ml of nitrobenzene were successively added 42.2 g (0.203 mol)Of 4a, 10a-dihydro-9,10-phenanthrenequinone and 300 mg (0.002 mol) of aluminum chloride,After stirring and heating to 105 ° C, 84.2 g (0.527 mol) of liquid bromine was added over 40 minutes and reacted for 3 hours.After cooling to room temperature, the crude product was filtered off and recrystallized from xylene to give 46.9 g (0.128 mol) of Intermediate A in a 63percent yield.
56.92%
With bromine In nitrobenzene at 120℃; for 3 h;
Preparation of Compound B; [98] Compound A (20 g, 96.05 mmol), benzoyl peroxide (3.1 g, 9.60 mmol, 75percent), nitrobenzene (300 mL) and Br2 (10.85 mL, 211.3 mmol) were mixed at room temperature and heated at 120°C. 3 hours later, the mixture was cooled to room temperature, neutralized with KOH solution and extracted with methylene chloride (MC). After distillation under reduced pressure, Compound B (20 g, 56.92 percent) was obtained by recrystallizing an obtained solid with ethyl acetate (EA).
Reference：
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[2] Journal of Materials Chemistry, 2012, vol. 22, # 10, p. 4383 - 4390
[3] Patent: WO2005/123754, 2005, A2, . Location in patent: Page/Page column 50-51; Sheet 28
[4] Chemistry - A European Journal, 2014, vol. 20, # 32, p. 10170 - 10178
[5] Journal of the American Chemical Society, 2014, vol. 136, # 1, p. 427 - 435
[6] RSC Advances, 2016, vol. 6, # 96, p. 94218 - 94227
[7] New Journal of Chemistry, 2017, vol. 41, # 2, p. 628 - 638
[8] Tetrahedron Letters, 2010, vol. 51, # 37, p. 4894 - 4897
[9] Chemical Communications, 2011, vol. 47, # 31, p. 8865 - 8867
[10] Journal of Organic Chemistry, 2011, vol. 76, # 23, p. 9660 - 9669
[11] Organic Letters, 2018,
[12] Organic Letters, 2011, vol. 13, # 6, p. 1326 - 1329
[13] Patent: CN104326971, 2016, B, . Location in patent: Paragraph 0071; 0072; 0073
[14] Patent: CN104447505, 2017, B, . Location in patent: Paragraph 0067; 0068; 0069
[15] Patent: CN106946898, 2017, A, . Location in patent: Page/Page column 0050; 0051
[16] Journal of Organic Chemistry, 2013, vol. 78, # 7, p. 3001 - 3008
[17] Journal of Organic Chemistry, 2009, vol. 74, # 21, p. 8484 - 8487
[18] Organic Letters, 2011, vol. 13, # 13, p. 3304 - 3307
[19] Organic and Biomolecular Chemistry, 2016, vol. 14, # 16, p. 3889 - 3905
[20] Organic Letters, 2014, vol. 16, # 3, p. 936 - 939
[21] Crystal Growth and Design, 2015, vol. 15, # 5, p. 2235 - 2242
[22] Arkivoc, 2011, vol. 2011, # 9, p. 15 - 37
[23] Journal of Materials Chemistry, 2011, vol. 21, # 5, p. 1404 - 1415
[24] Patent: US2016/64676, 2016, A1,
[25] Journal of Materials Chemistry, 2009, vol. 19, # 24, p. 4148 - 4156
[26] Journal of Organic Chemistry, 2010, vol. 75, # 20, p. 6858 - 6868
[27] Patent: CN107400129, 2017, A, . Location in patent: Paragraph 0070-0074
[28] Chemical Communications, 2018, vol. 54, # 14, p. 1786 - 1789
[29] Angewandte Chemie - International Edition, 2018, vol. 57, # 33, p. 10559 - 10563[30] Angew. Chem., 2018, vol. 130, p. 10719 - 10723,5
[31] Patent: WO2011/136484, 2011, A1, . Location in patent: Page/Page column 14-15
[32] Chemistry - An Asian Journal, 2011, vol. 6, # 11, p. 3001 - 3010
[33] Journal fuer Praktische Chemie (Leipzig), 1932, vol. <2> 134, p. 167,175
[34] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 10, p. 622
[35] Tetrahedron, 1964, vol. 20, p. 803 - 821
[36] Journal of the American Chemical Society, 2006, vol. 128, # 14, p. 4854 - 4864
[37] Journal of the American Chemical Society, 2007, vol. 129, # 36, p. 10994 - 10995
[38] Journal of the American Chemical Society, 2009, vol. 131, # 32, p. 11296 - 11297
[39] Organic Letters, 2013, vol. 15, # 6, p. 1162 - 1165
[40] Chemical Communications, 2014, vol. 50, # 64, p. 9003 - 9006
[41] Chemistry of Heterocyclic Compounds, 2014, vol. 50, # 6, p. 871 - 879[42] Khim. Geterotsikl. Soedin., 2014, # 6, p. 943 - 952,10
[43] Chemistry of Heterocyclic Compounds, 2014, vol. 50, # 6, p. 871 - 879[44] Khim. Geterotsikl. Soedin., 2014, vol. 50, # 6, p. 943 - 952,10
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[46] Patent: US9076971, 2015, B2, . Location in patent: Page/Page column 11-12
[47] Journal of Materials Chemistry C, 2016, vol. 4, # 17, p. 3798 - 3808
[48] Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13750 - 13755
[49] Patent: CN106905220, 2017, A, . Location in patent: Paragraph 0055; 0059; 0060
[50] Dyes and Pigments, 2017, vol. 146, p. 425 - 437
[51] Dyes and Pigments, 2018, vol. 159, p. 209 - 221
[52] Patent: US2018/273513, 2018, A1, . Location in patent: Paragraph 0176
[53] Journal of the American Chemical Society, 2018,
4
[ 84-11-7 ]
[ 84405-44-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With sulfuric acid; hydrogen bromide; bromine In water at 80℃; for 24 h;
3 grams of phenanthrene-9,10-diketone (manufactured by Aldrich Co., 95percent) was dissolved in 60 ml HBr and 20 ml H2SO4, and heated to 80° C., and a small amount of Br2 (manufactured by ACROS Co.) was added slowly, after which the mixture was allowed to react for 24 hours. After precipitation and filtration, dibromophenanthrene-9,10-diketone was obtained at a yield of more than 90percent. 2 grams of NaOH and 200 ml methanol was mixed and heated to about 60° C. After NaOH was dissolved completely, 3 grams of dibromophenanthrene-9,10-diketone and 4 grams of diethyl 1,3-acetonedicarboxylate (manufactured by ACROS Co., 95percent) were added and the temperature was maintained at 60° C. After 36 hours of reaction, 10percent HCl aqueous solution was added to the reaction mixture for neutralization, and then the mixture precipitated and filtered. The precipitate collected was dissolved by acetic acid, 300 ml 10percent HCl aqueous solution was added, and reaction took place for 18 hours at an elevated temperature. Then, acetic acid and water were removed, and the product neutralized with sodium hydrogen carbonate aqueous solution, precipitated, and filtered, giving Reactant 1 at a yield of 17percent. The following reaction scheme illustrates the preparation of Reactant 1: 3 grams of Reactant 1 and 150 ml ethylene glycol were mixed, 0.5 grams of N2H4 (manufactured by Lancaster Co., 98percent) was added, and the resulting mixture was stirred for 10 minutes, then 0.5 grams of KOH was added, and heated to about 180° C. for reaction. After 15 hours, the reaction mixture was cooled to room temperature and diluted with water, resulting in a white solid product (Compound 1), at a yield of 61percent, herein referred as 9,10:9,10-bis(trimethylene)-2,7-dibromo-9,10-dihydrophenanthrene. This Compound 1 is the novel phenanthrene compound of the present invention, and is also a mediate for the synthesis of various phenanthrene compounds of the present invention. 1H NMR (CDCl3): δ (ppm) about 1.40 (m, 2H), about 1.70 (m,2H), 1.88-1.96(m, 4H), 2.10-2.16(m, 4H), 7.23-7.26(m, 2H), 7.23-7.26(m, 2H), 7.92(s, 2H). The following reaction scheme illustrates the preparation of Compound 1:
85%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at -70℃; for 5 h; Inert atmosphere
Under a nitrogen atmosphere,41.64 g (200 mmol) of 4a,10a-dihydro-9,10-phenanthrenequinone was dissolved in 500 ml of anhydrous carbon tetrachloride,3.28 g (20 mmol) of azobisisobutyronitrile was added at -70 ° C,Then, 78.31 g (440 mmol) of NBS was added in four portions. The temperature was maintained and the reaction was continued for 5 hours.The reaction is completed, washed with distilled water, extracted with carbon dioxide, dried over anhydrous sodium sulfate, distilled under reduced pressure,Purification by column chromatography gave 62.22 g, (170 mmol) of Intermediate E in 85percent yield.
73%
With N-Bromosuccinimide In water; ethyl acetate
EXAMPLE 1 Synthesis of 6,11-bis(phenoxazin-10-yl)-1,4-diazatriphenylene (Compound 1) 9,10-Phenanthrenequinone (10 g) and concentrated sulfuric acid (100 mL) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen. N-bromosuccinimide (18 g) was added, and the mixture was stirred at a room temperature for 2 hours. After water (50 mL) was added, the mixture was added into ice water (600 mL). A precipitated solid was collected by filtration and washed under heat and reflux with ethyl acetate (100 mL) followed by vacuum drying to obtain a yellow solid of 2,7-dibromo-9,10-phenanthrenequinone (yield 73percent).
63%
at 20℃;
N-bromosuccinimide (19.6 g, 110 mmol) was added with smallportion to a solution of phenanthrene-9,10-dione (1) (10.4 g,50 mmol) in 500 ml of concentrated sulfuric acid and the mixturewas stirred overnight at room temperature. The reaction wasstopped by pouring into sufficient quantity of ice and then the solidcompound was filtered. The orange powder was washed withwater several times. Recrystallization from dimethyl sulfoxide(DMSO) gave the product as needle-like red crystals. (yield: 11.3 g,63percent).1H NMR (DMSO-d6, 400 MHz) δ= 7.93 (d, 2H), 8.05 (d, 2H),8.23 (d, 2H).
60%
Stage #1: for 0.25 h; Stage #2: for 24 h; Darkness
A solution of 9,10-phenanthrenequinone (20.8 g, 100 mmol) and concentrated sulfuric acid (300 ml) was added to a 500 ml three-necked round bottom flask and mechanically stirred for 15 minutes. Bromosuccinimide (NBS) (40 g, 220 mmol ).The reaction was carried out in the dark for 24 hours. After the completion of the reaction, the reaction was slowly poured into ice water, and the residue was washed several times with aqueous sodium bicarbonate, water and methanol.The residue was dried and rinsed with N, N-dimethylformamide (DMF) to give 22 g of an orange solid in 60percent yield.
53%
at 20 - 40℃; for 5 h; Inert atmosphere
a) 104 g (0.50 mol) of 9, 10-dioxophenanthrene are suspended under nitrogen in 2000 ml of sulfuric acid and treated in small portions with a total of 182.5 g (1.03 mol) of N- bromosuccinimide during one hour at a temperature below 40°C. The resulting red brown viscous reaction mass is stirred at room temperature for four hours. The reaction mixture is slowly dropped into 6000 ml of an ice-water mixture under slow stirring. The resulting or-ange suspension is filtered and the solid washed with 5000 ml of water and 2000 ml of eth- anol, and then dried under vacuum at 70°C. The orange solid is dissolved in 2100 ml N,N- dimethylformamide (DMF) under reflux and further stirred at 80°C for one hour. The resulting suspension is filtered at 80°C and the solid washed with 1000 ml of DMF and 600 ml of methanol, followed by drying under vacuum at 80°C, giving the title product as a red powder (yield: 96.8 g (53percent)). Melting point: 284-285°C.
50%
at 0℃; for 2 h;
Synthesis of Compound 15-1 In the three-necked flask, add phenanthraquinones (6.24g, 30mmol), concentrated sulfuric acid (50 ml), at 0 °C NBS (11.2g, 63mmol) is slowly added reaction 2 hours, the reaction solution slowly poured into ice water, filtered, the resulting solid with dimethyl sulfoxide recrystallization to obtain 5.6g orange solid, yield is 50percent.
50%
at 0℃; for 2 h;
In the three-necked flask,Is addedPhenanthrenequinone(6 · 24g, 30mmol), concentrated sulfuric acid (50ml), at 0 ° C and slowly added NBS (11.2g, 63mmol), 2 hours reaction, the reaction mixture was slowly poured into ice water, filtered, the cake washed with dimethylsulfoxide recrystallization sulfoneOrange solid 5.6g, 50percent yield.
Reference：
[1] Chemical Communications, 2014, vol. 50, # 32, p. 4172 - 4174
[2] Patent: US2005/176952, 2005, A1, . Location in patent: Page/Page column 5
[3] Patent: CN107400129, 2017, A, . Location in patent: Paragraph 0113-0114
[4] Organic Letters, 2012, vol. 14, # 10, p. 2564 - 2567
[5] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 8, p. 1714 - 1720
[6] Chemistry - A European Journal, 2014, vol. 20, # 32, p. 10170 - 10178
[7] Chemical Communications, 2018, vol. 54, # 14, p. 1786 - 1789
[8] Patent: US2016/64676, 2016, A1,
[9] Organic Electronics: physics, materials, applications, 2017, vol. 44, p. 238 - 246
[10] Patent: CN103724283, 2016, B, . Location in patent: Paragraph 0034-0036
[11] Patent: WO2013/104649, 2013, A1, . Location in patent: Page/Page column 42-43
[12] Patent: CN104073249, 2016, B, . Location in patent: Paragraph 0065; 0066; 0067
[13] Patent: CN104030988, 2016, B, . Location in patent: Paragraph 0061; 0063; 0069-0071
[14] Chemische Berichte, 1904, vol. 37, p. 3560
[15] Chemische Berichte, 1927, vol. 60, p. 1358
[16] Tetrahedron, 1964, vol. 20, p. 803 - 821
[17] Chemische Berichte, 1904, vol. 37, p. 3560
[18] Organic Electronics: physics, materials, applications, 2011, vol. 12, # 10, p. 1625 - 1631
[19] Chemical Communications, 2014, vol. 50, # 20, p. 2653 - 2656
[20] Chemistry of Heterocyclic Compounds, 2014, vol. 50, # 6, p. 871 - 879[21] Khim. Geterotsikl. Soedin., 2014, # 6, p. 943 - 952,10
[22] Chemistry of Heterocyclic Compounds, 2014, vol. 50, # 6, p. 871 - 879[23] Khim. Geterotsikl. Soedin., 2014, vol. 50, # 6, p. 943 - 952,10
[24] Journal of Materials Chemistry C, 2017, vol. 5, # 39, p. 10332 - 10342
5
[ 84-11-7 ]
[ 84405-44-7 ]
Reference：
[1] Chemische Berichte, 1927, vol. 60, p. 1360
6
[ 7732-18-5 ]
[ 7726-95-6 ]
[ 84-11-7 ]
[ 84405-44-7 ]
Reference：
[1] Chemische Berichte, 1904, vol. 37, p. 3560
7
[ 7647-01-0 ]
[ 98-71-5 ]
[ 84-11-7 ]
[ 84405-44-7 ]
Reference：
[1] Chemische Berichte, 1927, vol. 60, p. 1358
8
[ 84-11-7 ]
[ 216312-73-1 ]
Reference：
[1] Organic Letters, 2014, vol. 16, # 3, p. 936 - 939
[2] Patent: WO2015/103215, 2015, A1,
[3] Journal of Materials Chemistry C, 2016, vol. 4, # 17, p. 3798 - 3808
[4] Patent: CN106905220, 2017, A,
9
[ 84-11-7 ]
[ 887127-69-7 ]
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 14, p. 4854 - 4864
[2] Journal of the American Chemical Society, 2018,
With bromine; dibenzoyl peroxide; In nitrobenzene; for 3h;Irradiation;
1000-ml,45.0 g (0.216 mol) of phenanthrenequinone (Sub 1-1) was added to a four-neck round bottom flask,400 ml of nitrobenzene and 0.52 g (2.16 mmol) of benzoyl peroxide were added and stirred. 12.18 ml (0.238 mol) of bromine was slowly added thereto.The reaction solution was irradiated with light with a 200 W tungsten lamp to conduct photoreaction for 3 hours.The reaction solution was cooled to room temperature, vacuum filtered, washed with methanol, and the resulting solid was separated and stirred in methanol.The solid was vacuum-dried again by vacuum filtration to obtain 64.3 g (yield: 82%) of Sub 7-1.
61%
With acetic acid; dibenzoyl peroxide; at 106℃; for 3.25h;Inert atmosphere;
To 41.6g (0.20 mol) of 9,10-dioxo-phenanthrene was suspended under nitrogen in 500ml of acetic acid and 106 with 2.4g (0.01 mol) of dibenzoyl peroxide, whereafter in 75 minutes during the dropwise added 35.2g (0.22 mol) of bromine.During the addition was added dropwise over 75 minutes 35.2g (0.22 mol) of bromine was used during the addition was added dropwise over 45 minutes 25.6g (0.16 mol) of bromine.The reaction mixture was heated at 106 additional three hours, followed by stirring at room temperature for 20 hours.The yellow suspension was filtered, washed with a small amount of acetic acid, followed by washing with 500ml water and 500ml of ethanol.The remaining yellow solid (80g) was dissolved in hot N, N- dimethylformamide (DMF), and the solution was cooled to room temperature, until precipitation begins.The precipitate by stirring at room temperature for 1 hour to complete.The precipitated solid was filtered, washed with a small amount of methanol and DMF and the additional amount of hexane.At 50 deg.] C under vacuum to give a yellow powder after drying the title product (Yield: 34.8g (61%)).
24%
With bromine; dibenzoyl peroxide; In nitrobenzene; at 60℃; for 4h;Schlenk technique;
A compound A (9.25 g, 44.4 mmol) was charged in a 100 mL Schlenk tube, and then 20 mL of nitrobenzene was added thereto. Then, benzoyl peroxide (0.39 g, 1.61 mmol) was added thereto, and bromine (2.29 mL, 44.4 mmol) was added thereto dropwise. Then, the resultant was stirred while conducting heating for 4 hours at 60 C. Methanol was added to the resultant solution to precipitate a solid, and the solid was removed therefrom by filtration. The resulting solid was purified by silica gel column chromatography (developing solvent: toluene) to obtain a yellow solid (yield amount: 3.02 g, yield: 24%).Chemical shift values (delta) of the compound measured by 1H NMR (400 MHz, CDCl3) were as follows: delta 8.22 (dd, J=7.6, 1.6 Hz, 1H), 8.18 (d, J=1.6 Hz, 1H), 8.06 (d, J=8.4 Hz, 1H), 7.98 (d, J=8.0 Hz, 1H), 7.75 (td, J=7.6, 1.2 Hz, 1H), 7.62 (dd, J=8.4, 2.0 Hz, 1H), 7.53 (t, J=7.6 Hz, 1H). It was confirmed by 1H NMR measurement that the obtained compound was a compound B.
With bromine; dibenzoyl peroxide; In nitrobenzene; at 80℃; for 0.75h;Irradiation; Heating / reflux;
Step 3 : 3-bromophenanthrene-9,10-dioneTo a solution of 3-bromophenanthrene (486 mg, 1.29 mmol) from Step 2 above, in acetic acid (30 rnL) was added Cr?3 (800 mg, 8.0 mmol). The reaction was stirred at reflux for 1 hour, then cooled to room temperature and poured into water. The resulting suspension was stirred for 0.5 hour and filtered. The solids obtained were washed with water and hexanes. The solids were then swished in hexanes and filtered to afford 3-bromophenanthrene-9,10-dione (381 mg, 70%) as a yellow solid.This quinone could also be prepared by the following procedure :To a solution of phenanthrene-9, 10-dione (10 g, 48 mmol) in nitrobenzene (50 mL) was added benzoyl peroxide (480 mg, 2 mmol) and bromine (2.34 mL, 45 mmol). The reaction mixture was heated at 80 0C, while being irradiated with a sunlamp, for 45 minutes. The reaction mixture was cooled to room temperature. Ethyl acetate (150 mL) was added and the mixture triturated for 5 minutes. The resulting solids were filtered, washed with ethyl acetate and dried under high vacuum to afford 3- bromophenanthrene-9,10-dione (5.53 g) as a yellow solid.
With sulfuric acid; hydrogen bromide; bromine; In water; at 80℃; for 24h;
3 grams of phenanthrene-9,10-diketone (manufactured by Aldrich Co., 95%) was dissolved in 60 ml HBr and 20 ml H2SO4, and heated to 80 C., and a small amount of Br2 (manufactured by ACROS Co.) was added slowly, after which the mixture was allowed to react for 24 hours. After precipitation and filtration, dibromophenanthrene-9,10-diketone was obtained at a yield of more than 90%. 2 grams of NaOH and 200 ml methanol was mixed and heated to about 60 C. After NaOH was dissolved completely, 3 grams of dibromophenanthrene-9,10-diketone and 4 grams of diethyl 1,3-acetonedicarboxylate (manufactured by ACROS Co., 95%) were added and the temperature was maintained at 60 C. After 36 hours of reaction, 10% HCl aqueous solution was added to the reaction mixture for neutralization, and then the mixture precipitated and filtered. The precipitate collected was dissolved by acetic acid, 300 ml 10% HCl aqueous solution was added, and reaction took place for 18 hours at an elevated temperature. Then, acetic acid and water were removed, and the product neutralized with sodium hydrogen carbonate aqueous solution, precipitated, and filtered, giving Reactant 1 at a yield of 17%. The following reaction scheme illustrates the preparation of Reactant 1: 3 grams of Reactant 1 and 150 ml ethylene glycol were mixed, 0.5 grams of N2H4 (manufactured by Lancaster Co., 98%) was added, and the resulting mixture was stirred for 10 minutes, then 0.5 grams of KOH was added, and heated to about 180 C. for reaction. After 15 hours, the reaction mixture was cooled to room temperature and diluted with water, resulting in a white solid product (Compound 1), at a yield of 61%, herein referred as 9,10:9,10-bis(trimethylene)-2,7-dibromo-9,10-dihydrophenanthrene. This Compound 1 is the novel phenanthrene compound of the present invention, and is also a mediate for the synthesis of various phenanthrene compounds of the present invention. 1H NMR (CDCl3): delta (ppm) about 1.40 (m, 2H), about 1.70 (m,2H), 1.88-1.96(m, 4H), 2.10-2.16(m, 4H), 7.23-7.26(m, 2H), 7.23-7.26(m, 2H), 7.92(s, 2H). The following reaction scheme illustrates the preparation of Compound 1:
85%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at -70℃; for 5h;Inert atmosphere;
Under a nitrogen atmosphere,41.64 g (200 mmol) of 4a,10a-dihydro-9,10-phenanthrenequinone was dissolved in 500 ml of anhydrous carbon tetrachloride,3.28 g (20 mmol) of azobisisobutyronitrile was added at -70 C,Then, 78.31 g (440 mmol) of NBS was added in four portions. The temperature was maintained and the reaction was continued for 5 hours.The reaction is completed, washed with distilled water, extracted with carbon dioxide, dried over anhydrous sodium sulfate, distilled under reduced pressure,Purification by column chromatography gave 62.22 g, (170 mmol) of Intermediate E in 85% yield.
73%
With N-Bromosuccinimide; In water; ethyl acetate;
EXAMPLE 1 Synthesis of 6,11-bis(phenoxazin-10-yl)-1,4-diazatriphenylene (Compound 1) 9,10-Phenanthrenequinone (10 g) and concentrated sulfuric acid (100 mL) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen. N-bromosuccinimide (18 g) was added, and the mixture was stirred at a room temperature for 2 hours. After water (50 mL) was added, the mixture was added into ice water (600 mL). A precipitated solid was collected by filtration and washed under heat and reflux with ethyl acetate (100 mL) followed by vacuum drying to obtain a yellow solid of 2,7-dibromo-9,10-phenanthrenequinone (yield 73%).
68%
With N-Bromosuccinimide; sulfuric acid; at 20℃; for 18h;Sonication;
9,10-phenanthraquinone (5.00 g, 24.01 mmol, 1 .0 eq), N-bromosuccinimide, NBS, (9.40 g, 52.83 mmol, 2.2 eq) was added to a 500 ml_ round bottom flask equipped with a magnetic stir bar followed by sulfuric acid (138.8 ml_). The solution was stirred at room temperature for one hour, at which point the viscosity of the solution was high enough that the magnetic stir bar would not mix the solution. Thus the flask was lowered into an ultrasonic bath which lowered the viscosity and allowed the solution to continue mixing. The mixture was then stirred 17 h at room temperature. The reaction was quenched by pouring onto ice. The product was collected by vacuum filtration and rinsed with water. The crude was recrystallized from boiling DMSO. The pure product was filtered off and rinsed with water and dried under a low pressure vacuum, resulting in deep orange crystals. Yield 5.93 g (68 %). Figure 31 shows 1 HNMR (400 MHz, DMSO-d6, 25C) d (ppm) 8.25 (d, J = 8.6 Hz, 1 H), 8.08 (d, J = 2.3 Hz, 1 H), 7.96 (dd, J = 8.5, 2.3 Hz, 1 H) spectra of compound S5. Figure 32 shows 13C NMR (101 MHz, DMSO-de, 25C) d (ppm) 176.73, 137.36, 133.55, 133.12, 130.97, 126.90, 122.81 spectra of compound S5.
63%
With N-Bromosuccinimide; sulfuric acid; at 20℃;
N-bromosuccinimide (19.6 g, 110 mmol) was added with smallportion to a solution of phenanthrene-9,10-dione (1) (10.4 g,50 mmol) in 500 ml of concentrated sulfuric acid and the mixturewas stirred overnight at room temperature. The reaction wasstopped by pouring into sufficient quantity of ice and then the solidcompound was filtered. The orange powder was washed withwater several times. Recrystallization from dimethyl sulfoxide(DMSO) gave the product as needle-like red crystals. (yield: 11.3 g,63%).1H NMR (DMSO-d6, 400 MHz) delta= 7.93 (d, 2H), 8.05 (d, 2H),8.23 (d, 2H).
60%
A solution of 9,10-phenanthrenequinone (20.8 g, 100 mmol) and concentrated sulfuric acid (300 ml) was added to a 500 ml three-necked round bottom flask and mechanically stirred for 15 minutes. Bromosuccinimide (NBS) (40 g, 220 mmol ).The reaction was carried out in the dark for 24 hours. After the completion of the reaction, the reaction was slowly poured into ice water, and the residue was washed several times with aqueous sodium bicarbonate, water and methanol.The residue was dried and rinsed with N, N-dimethylformamide (DMF) to give 22 g of an orange solid in 60% yield.
53%
With N-Bromosuccinimide; sulfuric acid; at 20 - 40℃; for 5h;Inert atmosphere;
a) 104 g (0.50 mol) of 9, 10-dioxophenanthrene are suspended under nitrogen in 2000 ml of sulfuric acid and treated in small portions with a total of 182.5 g (1.03 mol) of N- bromosuccinimide during one hour at a temperature below 40C. The resulting red brown viscous reaction mass is stirred at room temperature for four hours. The reaction mixture is slowly dropped into 6000 ml of an ice-water mixture under slow stirring. The resulting or-ange suspension is filtered and the solid washed with 5000 ml of water and 2000 ml of eth- anol, and then dried under vacuum at 70C. The orange solid is dissolved in 2100 ml N,N- dimethylformamide (DMF) under reflux and further stirred at 80C for one hour. The resulting suspension is filtered at 80C and the solid washed with 1000 ml of DMF and 600 ml of methanol, followed by drying under vacuum at 80C, giving the title product as a red powder (yield: 96.8 g (53%)). Melting point: 284-285C.
50%
With N-Bromosuccinimide; sulfuric acid; at 0℃; for 2h;
Synthesis of Compound 15-1 In the three-necked flask, add phenanthraquinones (6.24g, 30mmol), concentrated sulfuric acid (50 ml), at 0 C NBS (11.2g, 63mmol) is slowly added reaction 2 hours, the reaction solution slowly poured into ice water, filtered, the resulting solid with dimethyl sulfoxide recrystallization to obtain 5.6g orange solid, yield is 50%.
50%
With N-Bromosuccinimide; sulfuric acid; at 0℃; for 2h;
In the three-necked flask,Is addedPhenanthrenequinone(6 · 24g, 30mmol), concentrated sulfuric acid (50ml), at 0 C and slowly added NBS (11.2g, 63mmol), 2 hours reaction, the reaction mixture was slowly poured into ice water, filtered, the cake washed with dimethylsulfoxide recrystallization sulfoneOrange solid 5.6g, 50% yield.
10.1 g (82 mmol) of <strong>[608-32-2]1,2,3-triaminobenzene</strong> and 4.6 g (70 mmol) of 9,10-phenanthrenequinone were placed in a four-necked flask, to which 350 g of a solvent of acetic acid and methanol at 1:1 was added for dissolution, followed by reaction at a reaction temperature of 70°C for 2 hours. After the reaction, the solvent was removed and the resulting product was washed with methanol to obtain the intended product. Yield: 17.1 g Ocher solid m/z: 295 (calculated: 295.11) 13C-NMR: 146.932, 144.145, 143.084, 139.740, 133.473, 133.007, 132.656, 132.213, 131.602, 131.488, 130.847, 130.473, 128.465, 126.869, 126.831, 126.663, 123.900, 116.243, 108.647 ppm
With indium; acetic acid; In methanol; for 0.133333h;Reflux; Inert atmosphere;
General procedure: 4.2. General procedure for the indium-mediated reductivecyclization of 2-nitroanilines to prepare quinoxalines A mixture of the 2-nitroaniline derivative (1.0 mmol), dione (1.0or 2.0 mmol), indium (0.574 g, 5.0 mmol), and acetic acid (0.300 g,5 mmol or 0.600 g,10 mmol) or indium chloride (0.221 g,1 mmol or0.265 g,1.2 mmol) in methanol (5 mL) or toluene (5 mL) was stirredat 50 C, 80 C, or reux under a nitrogen atmosphere. After com-pletion of the reaction, the reaction mixture was diluted with ethylacetate (30 mL), ltered through Celite, and the ltrate was pouredinto 10% NaHCO3 (30 mL) and extracted with ethyl acetate(30 mL3). The combined organic extracts were dried over MgSO4,ltered, and concentrated. The residue was eluted with ethyl ace-tate/hexane (v/v10/90) through a silica gel column to give thecorresponding pure quinoxaline. Quinoxaline structures werecharacterized by 1H NMR, 13C NMR, FTIR, and GCeMS, and weremostly known compounds. For unknown compounds, elementalanalysis data were additionally obtained. 4.2.1. 2,3-Dimethylquinoxaline (5).19,31aef Yield 87%. Yellow solid,mp 109e110 C (lit.31f mp 105 C). TLC (10% ethyl acetate/hexane) Rf0.30; 1H NMR (400 MHz, CDCl3) d 7.91 (dd, 2H, J6.3, 3.5 Hz), 7.59(dd, 1H, J6.3, 3.5 Hz), 2.66 (s, 6H); 13C NMR (100 MHz, CDCl3)d 153.4, 141.0, 128.7, 128.2, 23.1; IR (KBr) 3109, 3078, 3030, 2995,2953, 2914, 1490, 1398, 1164 cm1;GCeMS m/z (rel intensity) 158(M, 99), 117 (100), 76 (28), 50 (12).
With indium; acetic acid; In toluene; for 0.333333h;Reflux; Inert atmosphere;
General procedure: 4.2. General procedure for the indium-mediated reductivecyclization of 2-nitroanilines to prepare quinoxalines A mixture of the 2-nitroaniline derivative (1.0 mmol), dione (1.0or 2.0 mmol), indium (0.574 g, 5.0 mmol), and acetic acid (0.300 g,5 mmol or 0.600 g,10 mmol) or indium chloride (0.221 g,1 mmol or0.265 g,1.2 mmol) in methanol (5 mL) or toluene (5 mL) was stirredat 50 C, 80 C, or reux under a nitrogen atmosphere. After com-pletion of the reaction, the reaction mixture was diluted with ethylacetate (30 mL), ltered through Celite, and the ltrate was pouredinto 10% NaHCO3 (30 mL) and extracted with ethyl acetate(30 mL3). The combined organic extracts were dried over MgSO4,ltered, and concentrated. The residue was eluted with ethyl ace-tate/hexane (v/v10/90) through a silica gel column to give thecorresponding pure quinoxaline. Quinoxaline structures werecharacterized by 1H NMR, 13C NMR, FTIR, and GCeMS, and weremostly known compounds. For unknown compounds, elementalanalysis data were additionally obtained. 4.2.1. 2,3-Dimethylquinoxaline (5).19,31aef Yield 87%. Yellow solid,mp 109e110 C (lit.31f mp 105 C). TLC (10% ethyl acetate/hexane) Rf0.30; 1H NMR (400 MHz, CDCl3) d 7.91 (dd, 2H, J6.3, 3.5 Hz), 7.59(dd, 1H, J6.3, 3.5 Hz), 2.66 (s, 6H); 13C NMR (100 MHz, CDCl3)d 153.4, 141.0, 128.7, 128.2, 23.1; IR (KBr) 3109, 3078, 3030, 2995,2953, 2914, 1490, 1398, 1164 cm1;GCeMS m/z (rel intensity) 158(M, 99), 117 (100), 76 (28), 50 (12).
1-(1-(naphthalen-1-yl)-1H-phenanthro[9,10-d]imidazol-2-yl)naphthalen-3-ol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With ammonium acetate; titanium(IV) oxide; at 120℃;
General procedure: A mixture of hydroxyl naphthaldehyde (1mmol), phenanthrene-9,10-dione (1mmol), naphthylamine (1mmol), ammonium acetate (1mmol) and TiO2 (1mol%) was stirred at 120C with continuous stirring with a bar magnet. The progress of the reaction was monitored by TLC (Scheme S4). After completion of the reaction, 10ml ethyl acetate was added to the reaction mixture and shaken well to dissolve the organic components and the mass filtered to separate out TiO2 and the residue was washed with ethyl acetate. The solid TiO2 residue was further washed with hot acetone and then dried up. The product was purified by column chromatography using benzene:ethyl acetate (9:1) as the eluent. The newly synthesised phenanthrimidazoles have been characterized by 1H and 13C NMR and mass (MS) spectra.
With molybdophosphoric acid hydrate; In neat (no solvent); at 150℃; for 3.5h;
General procedure: Condensation reactions were carried out in the temperature range 25-150 C. The used molar ratios of reactants and catalyst were: 2/11.0-14.6; MPA/1 0.008-0.43. The course of the reactions was routinely monitored by TLC. A small sample of the reaction mixture (solventfree reactions: ca. 0.2 mg; reactions in solution: ca. 0.1 mL) was treated with CH2Cl2 (ca. 1 mL), sonicated and the supernatant was analyzedby TLC. Completion of the reaction was judged by the disappearance of the TLC spot of the reagent 1a-h. A few experiments were stopped before the complete disappearance of 1 (Table 1, entries 7and 12). Longer heating did not lead to decomposition of the reaction products 3. Procedure A. A fine powdered mixture (or a paste for liquids 2) of 1, MPA, and 2 placed in a Pyrex glass centrifuge tube (size: 107-109 mm, diameter: 16-17 mm, style type: rimless) was kept at 25-150 C until the reaction was complete. Occasionally the mixture was allowed to cool to r.t. in a desiccator and then was again finely pulverized.
With selenium; Selectfluor; In acetonitrile; at 80℃; for 24h;Sealed tube;
O-phenylacetophenone58.8 mg (0.30 mmol), selenium powder 2.4 mg (0.03 mmol),Selectfluor 318.6 mg (0.9 mmol) was added successively to a 25 mL pressure-tight sealed vessel and 3 mL of acetonitrile was added. The mixture was stirred at 80 C. The reaction was followed by TLC. After 24 hours, the reaction was diluted with 10 mL of dichloromethane. The filtrate was filtered to obtain a clear solution. The organic solvent was distilled off and the residue was purified by silica gel column chromatography. (eluent ratio: petroleum ether to ethyl acetate volume ratio of 10:1) was separated, and the eluate was collected and the solvent was distilled off to obtain phenanthrenequinone 48 mg (76% yield) as a red-brown solid.
With ammonium acetate; acetic acid; for 24h;Reflux; Inert atmosphere;
General procedure: In a round bottom flask 9,10-phenanthrenequinone, <strong>[33228-45-4]4-hexylaniline</strong>, arylaldehyde and ammonium acetate were taken. Acetic acid (150mL) used as a solvent and refluxed for 24h under nitrogen atmosphere. The reaction mixture was poured into water (200mL) and extracted with dichloromethane (2×200mL). The combined organic layers were washed with aqueous NaHCO3 and brine solution, dried over Na2SO4 and concentrated using rotavapor. The crude reaction mixture was purified by 100-200 silica gel column chromatography using n-hexane/dichloromethane mixture as a mobile phase.
With ammonium acetate; acetic acid; for 24h;Reflux; Inert atmosphere;
General procedure: In a round bottom flask 9,10-phenanthrenequinone, <strong>[33228-45-4]4-hexylaniline</strong>, arylaldehyde and ammonium acetate were taken. Acetic acid (150mL) used as a solvent and refluxed for 24h under nitrogen atmosphere. The reaction mixture was poured into water (200mL) and extracted with dichloromethane (2×200mL). The combined organic layers were washed with aqueous NaHCO3 and brine solution, dried over Na2SO4 and concentrated using rotavapor. The crude reaction mixture was purified by 100-200 silica gel column chromatography using n-hexane/dichloromethane mixture as a mobile phase.
With ammonium acetate; acetic acid; for 24h;Reflux; Inert atmosphere;
General procedure: In a round bottom flask 9,10-phenanthrenequinone, <strong>[33228-45-4]4-hexylaniline</strong>, arylaldehyde and ammonium acetate were taken. Acetic acid (150mL) used as a solvent and refluxed for 24h under nitrogen atmosphere. The reaction mixture was poured into water (200mL) and extracted with dichloromethane (2×200mL). The combined organic layers were washed with aqueous NaHCO3 and brine solution, dried over Na2SO4 and concentrated using rotavapor. The crude reaction mixture was purified by 100-200 silica gel column chromatography using n-hexane/dichloromethane mixture as a mobile phase.
With ammonium acetate; In acetic acid; for 12h;Reflux; Inert atmosphere;
General procedure: Refluxing of phenanthrene-9, 10-dione (4.8mmol) and boronic ester benzaldehyde (4.8mmol) with ammonium acetate (58.7mmol) in glacial acetic acid for 12h under argon atmosphere. The reaction mass was cooled to room temperature, solid was filtered, washed with water and ether then dried to give pale off-white solid. Yield 60%.
21g (1 eq, 0.096 mol) of phenanthrene-9,10-dione and 22g (1.1 eq, 0.106 mol) of <strong>[53348-04-2]phenanthrene-9,10-diamine</strong> were mixed and dissolved in 300 mL of acetic acid followed by heating under reflux for 12 hours. Then, the reaction solution was put into distilled water, and the obtained solid was filtered, washed several times with distilled water, The filtered solid was purified by column chromatography to give Compound A-1 22.9 g (Yield: 60%) of the title compound (Mw. 382.07).
General procedure: Benzil (0.42g, 2.0mmol) and <strong>[1289218-74-1]4-(1,2,2-triphenylvinyl)benzaldehyde</strong> (0.86g, 2.4mmol) were dissolved in anhydrous acetic acid (30mL) at room temperature. 2-(4-Aminophenyl) acetonitrile (0.4g, 3.0mmol) was dissolved in glacial acetic acid (5mL) and was gradually added into this mixture solution. The mixture was stirred for 2h at 25C. Then, ammonium acetate (0.62g, 8.0mmol) was added and the mixture was heated to 120C for 12h. The final mixture was poured into brine (200mL) and was neutralized with NaOH aqueous solution. A large amount of precipitate was filtered, and washed with ethanol to afford green compound 1 (1.03g, 1.26mmol).
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