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Structure of 91371-12-9 * Storage: {[proInfo.prStorage]}
* 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.
With copper In N,N-dimethyl-formamide at 125℃; for 1 h; Inert atmosphere
(1) Under a nitrogen atmosphere, the compound No(1) (14.1 g, 50 mmol) and copper powder (7.0 g, 109 mmo 1) were dissolved in 55 mL of N, N-dimethylformamide, The mixture was stirred at 125 ° C for 1 hour and then stopped. After cooling, the residue is filtered and the residue is washed with an appropriate amount of toluene to ensure that the product is dissolved in the filtrate and the filtrate is subjected to vacuum distillation to obtain a crude product. The product was separated by silica gel column chromatography and separated in vacuo using petroleum ether and dichloromethane (ν / ν, 4/1) as eluent to give a yellow solid in 91percent yield and subjected to 1H NMR Characterization, confirming that the yellow solid was compound No(2)
88%
With copper In N,N-dimethyl-formamide at 125℃; for 5 h;
Compound B-1 (50. 0g, 179mmol) was dissolved in DMF (200mL) , and copper powder (27. 0g, 424_1) is added. At 125 ° C and the mixture was stirred for 3 hours. The reaction mixture was cooled to room temperature, filtered and the precipitate was removed after drying. With Me0H (500mL) and washed to give Compound B-2 (27.1g, 88percent).
88%
With copper In N,N-dimethyl-formamide at 125℃; for 3 h;
50.0 g (179 mmol) of 1,4-dibromo-2-nitrobenzene was dissolved in 200 mL of dimethylformamide (DMF) and 27.0 g (424 mmol) of copper powder was added thereto. The mixture was stirred at a temperature of about 125° C. for about 3 hours. The reaction mixture was cooled to room temperature, and then subjected to filtration to remove the precipitate therefrom. The resultant solid was dried, then washed with 500 mL of MeOH, thereby producing 27.1 g (yield: 88percent) of Intermediate 4-1.
88%
With copper In N,N-dimethyl-formamide at 125℃; for 3 h;
50.0 g (179 mmol) of the compound B-1 was dissolved in 200 mL of DMF, 27.0 g (424 mmol) of copper powder was added and the mixture was stirred at 125 °C for 3 hours. The reaction mixture was cooled to room temperature and the precipitate was filtered off and dried. And washed with 500 mL of MeOH to obtain 27.1 g (88percent) of the compound B-2.
Reference：
[1] Journal of Materials Chemistry C, 2015, vol. 3, # 11, p. 2624 - 2631
[2] Journal of Materials Chemistry A, 2016, vol. 4, # 22, p. 8750 - 8754
[3] Patent: CN104311588, 2016, B, . Location in patent: Paragraph 0026; 0027
[4] Journal of the American Chemical Society, 2005, vol. 127, # 21, p. 7662 - 7663
[5] Patent: CN103819455, 2016, B, . Location in patent: Paragraph 0067; 0068; 0069
[6] Patent: US2017/69856, 2017, A1, . Location in patent: Paragraph 0223-0224
[7] Patent: KR2015/34146, 2015, A, . Location in patent: Paragraph 0059-0061
[8] European Journal of Medicinal Chemistry, 1999, vol. 34, # 3, p. 215 - 224
[9] Journal of the American Chemical Society, 2006, vol. 128, # 28, p. 9034 - 9035
[10] Journal of the American Chemical Society, 2008, vol. 130, # 24, p. 7670 - 7685
[11] Organic Electronics: physics, materials, applications, 2018, vol. 59, p. 77 - 83
[12] Journal of the American Chemical Society, 2014, vol. 136, # 32, p. 11276 - 11279
[13] Journal of Materials Chemistry, 2011, vol. 21, # 32, p. 11800 - 11814
[14] Journal of Materials Chemistry C, 2015, vol. 3, # 26, p. 6822 - 6830
[15] Tetrahedron, 2003, vol. 59, # 17, p. 3131 - 3156
[16] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6248 - 6250
[17] Polymer, 2011, vol. 52, # 26, p. 6011 - 6019
[18] Journal of the American Chemical Society, 2018,
[19] Molecular Crystals and Liquid Crystals, 2006, vol. 459, # 1, p. 85/[365]-94/[374]
[20] Patent: US2005/225235, 2005, A1,
[21] Chemistry - An Asian Journal, 2015, vol. 10, # 10, p. 2134 - 2138
[22] Journal of the Chemical Society, 1938, p. 967,972
[23] Journal of the Chemical Society, 1932, p. 285,296
[24] Chemische Berichte, 1901, vol. 34, p. 2176
[25] Journal of the Chemical Society, 1961, p. 5029 - 5037
[26] Journal of the Chemical Society [Section] C: Organic, 1970, p. 1967 - 1973
[27] Patent: EP2266982, 2010, A1, . Location in patent: Page/Page column 43-45
[28] Journal of Materials Chemistry C, 2014, vol. 2, # 24, p. 4835 - 4846
[29] Chemical Communications, 2016, vol. 52, # 21, p. 4022 - 4024
[30] Journal of the American Chemical Society, 2018, vol. 140, # 24, p. 7611 - 7622
2
[ 83834-10-0 ]
[ 91371-12-9 ]
Yield
Reaction Conditions
Operation in experiment
84%
With FeCl3 In 1-methyl-pyrrolidin-2-one; hydrogenchloride
3,7-Dicyanodibenzothiophene (14). A refluxing solution of 3,7-dibromodibenzothiophene (13, 1.56 g, 4.56 mmol) and copper(I) cyanide (1.27 g, 14.2 mmol) in 1-methyl-2-pyrrolidinone (10 mL) was stirred under nitrogen for 3 h. The cooled reaction mixture was treated with a solution of FeCl3 (3.29 g) in conc. HCl (10 mL). After the initial exotherm, the mixture was stirred with heat for 1 h. The mixture was poured over ice. The resultant gray precipitate was filtered off, dried, and sublimed (280° C., 0.3 mm Hg) to give white powder (0.89 g, 84percent): mp >330° C.; 1H NMR (400 MHz, DMSO-d6) δ 8.76 (s, 2 H), 8.71 (d, J=8.2 Hz, 2 H), 8.01 (dd, J=8.2 and 1.4 Hz, 2 H); HPLC (method B)tR 16.84 min (93.5 area percent). Anal. (C14H6N2S.0.25H2O) C, H, N.
Reference：
[1] Journal of the Chemical Society, 1932, p. 285,296
7
[ 91371-12-9 ]
[ 136630-36-9 ]
Yield
Reaction Conditions
Operation in experiment
85%
With hydrogenchloride; tin In ethanol; water at 70℃; for 1 h; Inert atmosphere
(2) Under a nitrogen atmosphere, Compound 2 (4.02 g, 10 mmol) was dissolved in 48 mL of ethanol and 30 mL of an aqueous solution, tin powder (5.94 g, 50 mmol) was slowly added with stirring and then heated at 70 ° C for 1 hour , The heating was stopped and the reaction flask was placed in an ice-water bath, and 2 mol / L aqueous sodium hydroxide solution was gradually added thereto until the reaction system became alkaline. Then extracted with dichloromethane, the organic phase was collected and dried over anhydrous sodium sulfate. The product was separated by silica gel column chromatography and separated in vacuo using petroleum ether and tetrahydrofuran (ν / ν, 20/1) as eluent to give a pale gray solid in 85percent yield using 1H NMR. The yellow solid was confirmed to be compound 3
72%
With hydrogenchloride; tin In ethanol; water at 100℃; for 2 h;
Compound B-2 (15g, 37.3mmol) dissolved in ethanol (200 ml) in, and adding 32percent (w/w) HCl aqueous solution (120 ml). At room temperature for 10 minutes by adding tin powder batches (17.6g, 147mmol), for 100 °C stirring 2 hours. After cooling at room temperature, the reaction mixture is added to ice water, the use of 20percent (w/w) NaOH aqueous solution (150 ml) to become alkaline. Diethyl ether for extraction, salt water (bryn) washing and drying. Recrystallization from ethanol to obtain compound B-3 (9.2g, 72percent).
72%
With hydrogenchloride; tin In ethanol; water at 100℃; for 2 h;
15 g (37.3 mmol) of Intermediate 4-1 was dissolved in 200 mL of ethanol, and 120 mL of a 32percent (w/w) HCl aqueous solution was added thereto. At room temperature, 17.6 g (147 mmol) of tin powder was added portionwise thereto and stirred at a temperature of about 100° C. for about 2 hours. The resulting mixture was cooled to room temperature, and then added to ice water. 150 mL of a 20percent (w/w) NaOH aqueous solution was added thereto to make the resultant solution to have a basic pH. An extraction process was performed thereon using diethyl ether, and then, the resultant was washed with brine, dried, and then recrystallized using ethanol, thereby producing 9.2 g (yield: 72percent) of Intermediate 4-2.
72%
Stage #1: With hydrogenchloride; tin In ethanol; water for 0.166667 h; Stage #2: at 100℃; for 2 h;
15 g (37.3 mmol) of the compound B-2 was dissolved in 200 mL of ethanol and 120 mL of 32percent (w/w) HCl aqueous solution was added. The tin powder 17.6g (147mmol) was stirred for 10 min and portion-wise over 2 hours at 100 °C at room temperature. The reaction mixture was cooled to room temperature and poured into ice water. And made into a base state using 150 mL of 20percent (w/w) NaOH aqueous solution. The mixture was extracted with diethyl ether, washed with brine, dried and recrystallized from ethanol to obtain 9.2 g (72percent) of compound B-3.
Reference：
[1] Journal of Materials Chemistry A, 2016, vol. 4, # 22, p. 8750 - 8754
[2] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6248 - 6250
[3] Journal of the American Chemical Society, 2006, vol. 128, # 28, p. 9034 - 9035
[4] Journal of Materials Chemistry, 2011, vol. 21, # 32, p. 11800 - 11814
[5] Molecular Crystals and Liquid Crystals, 2006, vol. 459, # 1, p. 85/[365]-94/[374]
[6] Journal of Materials Chemistry C, 2015, vol. 3, # 26, p. 6822 - 6830
[7] Journal of the American Chemical Society, 2018,
[8] Journal of Materials Chemistry C, 2015, vol. 3, # 11, p. 2624 - 2631
[9] Patent: CN104311588, 2016, B, . Location in patent: Paragraph 0028
[10] Journal of the American Chemical Society, 2014, vol. 136, # 32, p. 11276 - 11279
[11] Journal of the American Chemical Society, 2005, vol. 127, # 21, p. 7662 - 7663
[12] Patent: CN103819455, 2016, B, . Location in patent: Paragraph 0067; 0070; 0071
[13] Patent: US2017/69856, 2017, A1, . Location in patent: Paragraph 0223; 0225
[14] Patent: KR2015/34146, 2015, A, . Location in patent: Paragraph 0059; 0062; 0063
[15] Patent: US2005/225235, 2005, A1,
[16] Organic Electronics: physics, materials, applications, 2018, vol. 59, p. 77 - 83
[17] Tetrahedron, 2003, vol. 59, # 17, p. 3131 - 3156
[18] Journal of the American Chemical Society, 2008, vol. 130, # 24, p. 7670 - 7685
[19] Patent: EP2266982, 2010, A1, . Location in patent: Page/Page column 44-45
[20] Chemistry - An Asian Journal, 2015, vol. 10, # 10, p. 2134 - 2138
[21] Chemical Communications, 2016, vol. 52, # 21, p. 4022 - 4024
[22] Journal of the American Chemical Society, 2018, vol. 140, # 24, p. 7611 - 7622
8
[ 91371-12-9 ]
[ 136630-36-9 ]
[ 79580-35-1 ]
Reference：
[1] European Journal of Medicinal Chemistry, 1997, vol. 32, # 10, p. 781 - 793
9
[ 91371-12-9 ]
[ 136630-39-2 ]
Reference：
[1] Molecular Crystals and Liquid Crystals, 2006, vol. 459, # 1, p. 85/[365]-94/[374]
[2] European Journal of Medicinal Chemistry, 1997, vol. 32, # 10, p. 781 - 793
[3] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6248 - 6250
10
[ 91371-12-9 ]
[ 852138-89-7 ]
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 28, p. 9034 - 9035
[2] Journal of the American Chemical Society, 2005, vol. 127, # 21, p. 7662 - 7663
[3] Journal of Materials Chemistry, 2011, vol. 21, # 32, p. 11800 - 11814
[4] Journal of Materials Chemistry C, 2015, vol. 3, # 11, p. 2624 - 2631
[5] Chemistry - An Asian Journal, 2015, vol. 10, # 10, p. 2134 - 2138
[6] Journal of Materials Chemistry C, 2015, vol. 3, # 26, p. 6822 - 6830
[7] Chemical Communications, 2016, vol. 52, # 21, p. 4022 - 4024
[8] Journal of Materials Chemistry A, 2016, vol. 4, # 22, p. 8750 - 8754
[9] Patent: CN103819455, 2016, B,
[10] Patent: US2017/69856, 2017, A1,
[11] Patent: KR2015/34146, 2015, A,
[12] Patent: CN104311588, 2016, B,
[13] Organic Electronics: physics, materials, applications, 2018, vol. 59, p. 77 - 83
11
[ 91371-12-9 ]
[ 891182-24-4 ]
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 28, p. 9034 - 9035
[2] Journal of Materials Chemistry, 2011, vol. 21, # 32, p. 11800 - 11814
12
[ 91371-12-9 ]
[ 958293-23-7 ]
Reference：
[1] Journal of Materials Chemistry, 2011, vol. 21, # 32, p. 11800 - 11814
With copper; In N,N-dimethyl-formamide;Inert atmosphere; Heating;
Under a N2 atmosphere, the mixture of 1,4-dibromo-2-nitrobenzene (5.0 g, 17.8 mmol), pre-washed copper powder (2.5 g, 38.8 mmol) and DMF (30 mL) were stirred at 125 C for 4 h. After cooling to room temperature, the reaction mixture was poured into ice water (100 mL), The precipitate was filtered and washed with water (5×20 mL). The crude product was purified by column chromatography silica gel with petroleum ether/CH2Cl2 (3/1, v/v) to obtain yellow solid (3.3 g, 92%). 1H NMR (400 MHz, CDCl3): delta (ppm) 8.38 (d, J = 2.0 Hz, 2H), 7.59 (dd, J = 8.4, 2.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H).
91%
With copper; In N,N-dimethyl-formamide; at 125℃; for 1h;Inert atmosphere;
(1) Under a nitrogen atmosphere, the compound No(1) (14.1 g, 50 mmol) and copper powder (7.0 g, 109 mmo 1) were dissolved in 55 mL of N, N-dimethylformamide, The mixture was stirred at 125 C for 1 hour and then stopped. After cooling, the residue is filtered and the residue is washed with an appropriate amount of toluene to ensure that the product is dissolved in the filtrate and the filtrate is subjected to vacuum distillation to obtain a crude product. The product was separated by silica gel column chromatography and separated in vacuo using petroleum ether and dichloromethane (nu / nu, 4/1) as eluent to give a yellow solid in 91% yield and subjected to 1H NMR Characterization, confirming that the yellow solid was compound No(2)
88%
With copper; In N,N-dimethyl-formamide; at 125℃; for 5h;
Compound B-1 (50. 0g, 179mmol) was dissolved in DMF (200mL) , and copper powder (27. 0g, 424_1) is added. At 125 C and the mixture was stirred for 3 hours. The reaction mixture was cooled to room temperature, filtered and the precipitate was removed after drying. With Me0H (500mL) and washed to give Compound B-2 (27.1g, 88%).
88%
With copper; In N,N-dimethyl-formamide; at 125℃; for 3h;
50.0 g (179 mmol) of 1,4-dibromo-2-nitrobenzene was dissolved in 200 mL of dimethylformamide (DMF) and 27.0 g (424 mmol) of copper powder was added thereto. The mixture was stirred at a temperature of about 125 C. for about 3 hours. The reaction mixture was cooled to room temperature, and then subjected to filtration to remove the precipitate therefrom. The resultant solid was dried, then washed with 500 mL of MeOH, thereby producing 27.1 g (yield: 88%) of Intermediate 4-1.
88%
With copper; In N,N-dimethyl-formamide; at 125℃; for 3h;
50.0 g (179 mmol) of the compound B-1 was dissolved in 200 mL of DMF, 27.0 g (424 mmol) of copper powder was added and the mixture was stirred at 125 C for 3 hours. The reaction mixture was cooled to room temperature and the precipitate was filtered off and dried. And washed with 500 mL of MeOH to obtain 27.1 g (88%) of the compound B-2.
77.7%
With copper; In N,N-dimethyl-formamide; at 125℃; for 3h;
250 g (0.890 mol) of 2,5-dibromonitrobenzene, 135.74 g (2.136 mol) of copper powder and 1 L of DMF were placed.The temperature within the reactor was elevated to 125 was stirred for 3 hours.When the reaction is completed, the temperature is lowered to room temperature,Toluene (500 mL) was added and stirred. The insoluble inorganic salts were removed by celite filtration and the filtrate was dried. To the dried filtrate, 2 L of methanol was added and stirred vigorously. The resulting crystals were filtered and dissolved again in 500 mL of toluene. The remaining inorganic salts were removed by celite filtering,The filtrate was dried, and further MeOH was added thereto to vigorously stir to obtain 139 g (yield 77.7%) of 4,4'-dibromo-2,2'-dinitro-biphenyl by recrystallization.
77.7%
With copper; In N,N-dimethyl-formamide; at 125℃; for 3h;
250 g (0.890 mol) of 2,5-dibromonitrobenzene, 135.74 g (2.136 mol) of copper powder and 1 L of DMF were added. The temperature of the reactor was raised to 125 C. and stirred for 3 hours. After the reaction was completed, the temperature was lowered to room temperature, and 500 mL of toluene was added thereto and stirred. The inorganic salts are insoluble was removed by celite filter, and the filtrate was dried. 2 liters of methanol was added to the dried filtrate and stirred vigorously. The resulting crystals were filtered and dissolved again in 500 mL of toluene. After removing the remaining inorganic salts by celite filter, The filtrate was dried and added again with MeOH, The mixture was vigorously stirred and recrystallized to obtain 139 g (77.7%) of 4,4'-dibromo-2,2'-dinitro-biphenyl.
77.7%
With copper; In N,N-dimethyl-formamide; at 125℃; for 3h;
250 g (0.890 mol) of 2,5-dibromonitrobenzene, 135.74 g (2.136 mol) of copper powder and 1 L of DMF were added.The temperature of the reactor was raised to 125 C. and stirred for 3 hours.After the reaction was completed, the temperature was lowered to room temperature, and 500 mL of toluene was added thereto and stirred.Insoluble inorganic salts were removed by celite filter and the filtrate was dried.2 liters of Methanol was added to the dried filtrate and stirred vigorously.The resulting crystals were filtered and dissolved again in 500 mL of Toluene.After removing the remaining inorganic salts by celite filter,Dry the filtrate and add MeOH again and recrystallize by strong stirring 139 g (77.7%) of 4,4'-Dibromo-2,2'-dinitro-biphenyl was obtained.
60%
In N-methyl-acetamide;
PREPARATION EXAMPLE 5 Preparation of the Starting Material Represented by Formula e 2,5-dibromonitrobenzene (12.0 g, 42.7 mmol) was dissolved in dimethylformamide (DMF, 80 ml), Cu (6.0 g, 93.94 mmol) was added thereto, and then the reaction mixture was reacted at 1200C for 3 hours. The reaction mixture was cooled to room temperature, the insoluble material was filtered off and the filtrate was concentrated. The resultant product was recrystallized in ethanol to obtain 4,4'-dibromo-2,2'-dinitrobiphenyl (10.2 g, 60%). MS [M+] 354.
38%
With copper; In N,N-dimethyl-formamide; at 137℃; for 2h;
1,4-Dibromo-2-nitrobenzene (25 g, 89 mmol) and copper powder (12.5 g, 197 mmol)Add to 150 mL of N,N-dimethylformamide (DMF)The mixture was heated to 137 C for 2 hours. After the reaction is completed, it is cooled to room temperature.Quenched with water. The reaction solution was extracted with ethyl acetate, and the organic layer was washed with brine.Dry with sodium sulfate. After passing through a chromatography column (hexane/ethyl acetate), a solid powder (13.6 g, 38%) was obtained.
With copper; In N,N-dimethyl-formamide; at 130℃; for 7h;Inert atmosphere;
Synthesis Example 10; Compound A-8 was synthesized by the method illustrated in Scheme 10.; To 230 ml of dimethylformamide were added 50.25 g of compound (10-a) (producedbyWako Pure Chemical Industries, Ltd.) and 25 g of copper powder (produced by Wako Pure Chemical Industries, Ltd.), and the resulting mixture was stirred under a nitrogen atmosphere at 130C for 7 hours. The solvent was distilled off under reduced pressure and then 500 ml of toluene was added, and the resulting mixture was filtrated with sellite, and a filtrate was washed with 400 ml of water and 200 ml of an aqueous solution of sodium hydrogen carbonate in this order and then dried with magnesium sulfate. After distilling off the solvent from the resulting solution, the solution was washed with 300 ml of isopropanol to obtain 26 g of compound (10-b).
With copper; In N,N-dimethyl-formamide; at 125℃; for 3.5h;Inert atmosphere;
In a 250 ml round bottom flask, 2.5-dibromonitrobenzene (15 mmol) and Cu (7 mmol) were added to dry DMF (100 ml), and the reaction was performed at 125 C for 3.5 hours under a nitrogen atmosphere. The obtained intermediate was mixed The solution was added to water, then filtered through a pad of celite, the filtrate was extracted with dichloromethane, then washed with water, dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to obtain intermediate 4, 4-dibromo-2,2-dinitrobenzene.
<strong>[91371-12-9]4,4'-dibromo-2,2'-dinitrobiphenyl</strong>(11g, 27.4 mmol) was dissolved in 135 mL of ethanol.78 mL of saturated hydrochloric acid having a concentration of 32% was added.Tin powder (13g, 108.5mmol) was added to the reaction solution several times in 10 minutes.The reaction was then refluxed for 2 hours. After the reaction is completed, the reaction solution is poured into ice water.The addition of a 20% by mass aqueous solution of sodium hydroxide is the pH of the mixture to around 9.0. The product was extracted with diethyl ether, washed with brine and dried over sodium sulfate. Filtration and concentration gave a brown solid (8.25 g, 88%).
85%
With hydrogenchloride; tin; In ethanol; water; at 70℃; for 1h;Inert atmosphere;
(2) Under a nitrogen atmosphere, Compound 2 (4.02 g, 10 mmol) was dissolved in 48 mL of ethanol and 30 mL of an aqueous solution, tin powder (5.94 g, 50 mmol) was slowly added with stirring and then heated at 70 C for 1 hour , The heating was stopped and the reaction flask was placed in an ice-water bath, and 2 mol / L aqueous sodium hydroxide solution was gradually added thereto until the reaction system became alkaline. Then extracted with dichloromethane, the organic phase was collected and dried over anhydrous sodium sulfate. The product was separated by silica gel column chromatography and separated in vacuo using petroleum ether and tetrahydrofuran (nu / nu, 20/1) as eluent to give a pale gray solid in 85% yield using 1H NMR. The yellow solid was confirmed to be compound 3
73.8%
With hydrogenchloride; tin; In ethanol; water; at 0 - 100℃; for 3h;
139.7 g (0.347 mol) of <strong>[91371-12-9]4,4'-dibromo-2,2'-dinitro-biphenyl</strong> was added and 2 L of ethanol was added.Then 1 L of 12 M HCl was added and stirred.The temperature of the reactor was lowered to 0 C and 165 g (1.39 mol) of Tin powder was added slowly over 20 minutes. The temperature of the reactor was raised to 100 C and refluxed for 3 hours. When the reaction was completed, the temperature of the reactor was lowered to 0 C. and 12 M 1 L of sodium hydroxide aqueous solution was slowly added to make the reaction solution basic. Ethylacetate was added to extract the organic layer, and the organic layer was dried and concentrated.Hexane and methylene chloride were used as a developing solvent to separate 4,4'-dibromo-2,2'-diaminobiphenyl (87.7 g, yield 73.8%) by column chromatography.
73.8%
With hydrogenchloride; tin; In ethanol; water; at 0 - 100℃; for 3.33333h;
139.7 g (0.347 mol) of <strong>[91371-12-9]4,4'-dibromo-2,2'-dinitro-biphenyl</strong> was added thereto, followed by 2 L of ethanol and 1L of 12 M HCl was added and stirred. The temperature of the reactor was lowered to 0 C. and 165 g (1.39 mol) Tin powder was slowly added over 20 minutes. The temperature of the reactor was raised to 100 C. and refluxed for 3 hours. After the reaction was completed, the temperature of the reactor was lowered to 0 C. and 1L of 12M aqueous sodium hydroxide solution was added slowly to make the reaction solution basic. Ethylacetate was added to extract the organic layer, and the organic layer was anhydrous and concentrated. Hexane and methylene chloride were used as developing solvents to separate the residue by column chromatography to obtain 4,4'-dibromo-2,2'-diaminobiphenyl. (87.7 g, 73.8%)
73.8%
With hydrogenchloride; tin; In ethanol; water; at 0 - 100℃; for 3.33h;
139.7 g (0.347 mol) of <strong>[91371-12-9]4,4'-dibromo-2,2'-dinitro-biphenyl</strong> was added thereto, followed by 2 L of ethanol.And 1 M of 12 M HCl was added and stirred. The temperature of the reactor was lowered to 0 C. and 165 g (1.39 mol) Tin powder was slowly added over 20 minutes.The temperature of the reactor was raised to 100 C. and refluxed for 3 hours.After the reaction was completed, the temperature of the reactor was lowered to 0 C., 12 M and 1 L of aqueous sodium hydroxide solution were added slowly to make the reaction solution basic.Ethylacetate was added to extract the organic layer, and the organic layer was anhydrous and concentrated.Hexane and methylene chloride were used as developing solvents to separate the residue by column chromatography to obtain 4,4'-dibromo-2,2'-diaminobiphenyl. (87.7 g, 73.8%)
72%
With hydrogenchloride; tin; In ethanol; water; at 100℃; for 2h;
Compound B-2 (15g, 37.3mmol) dissolved in ethanol (200 ml) in, and adding 32% (w/w) HCl aqueous solution (120 ml). At room temperature for 10 minutes by adding tin powder batches (17.6g, 147mmol), for 100 C stirring 2 hours. After cooling at room temperature, the reaction mixture is added to ice water, the use of 20% (w/w) NaOH aqueous solution (150 ml) to become alkaline. Diethyl ether for extraction, salt water (bryn) washing and drying. Recrystallization from ethanol to obtain compound B-3 (9.2g, 72%).
72%
With hydrogenchloride; tin; In ethanol; water; at 100℃; for 2h;
15 g (37.3 mmol) of Intermediate 4-1 was dissolved in 200 mL of ethanol, and 120 mL of a 32% (w/w) HCl aqueous solution was added thereto. At room temperature, 17.6 g (147 mmol) of tin powder was added portionwise thereto and stirred at a temperature of about 100 C. for about 2 hours. The resulting mixture was cooled to room temperature, and then added to ice water. 150 mL of a 20% (w/w) NaOH aqueous solution was added thereto to make the resultant solution to have a basic pH. An extraction process was performed thereon using diethyl ether, and then, the resultant was washed with brine, dried, and then recrystallized using ethanol, thereby producing 9.2 g (yield: 72%) of Intermediate 4-2.
72%
15 g (37.3 mmol) of the compound B-2 was dissolved in 200 mL of ethanol and 120 mL of 32% (w/w) HCl aqueous solution was added. The tin powder 17.6g (147mmol) was stirred for 10 min and portion-wise over 2 hours at 100 C at room temperature. The reaction mixture was cooled to room temperature and poured into ice water. And made into a base state using 150 mL of 20% (w/w) NaOH aqueous solution. The mixture was extracted with diethyl ether, washed with brine, dried and recrystallized from ethanol to obtain 9.2 g (72%) of compound B-3.
70%
With tin(II) chloride dihdyrate; In ethanol; at 90℃; for 12h;Inert atmosphere;
4,4'-Dibromo-2,2'-dinitrobiphenyl (3.0 g, 7.5 mmol) and SnCl2·2H2O (27.1 g, 120.0 mmol) were mixed in EtOH (30 mL) and stirred at 90 C for 12 h. After cooling to room temperature, the mixture was poured into 100 mL of ice water and added saturated NaOH solution to pH ~9. Then, the precipitation was collected by filtration to get brown solid (1.78 g, 70%). 1H NMR (400 MHz, CDCl3): delta (ppm) 6.93 (m, 6H), 3.74 (s, 4H).
67%
In hydrogenchloride; ethanol;
<strong>[91371-12-9]4,4'-dibromo-2,2'-dinitrobiphenyl</strong> (6.1 g, 15.17 mmol) was stirred in HCl 30 ml/EtOH 75 ml, Sn powder (7.2 g, 60.68 mmol) was added thereto, and then the reaction mixture was refluxed for 24 hours. Next, the reaction mixture was cooled to room temperature, neutralized with 10% NaOH solution, and then recrystallized in ethanol to obtain 4,4'-dibromo-2,2'-diaminobiphenyl (3.5 g, 67%). MS [M+H] 341.
To 320 ml of ethanol was added 26 g of the compound (10-b), and then 180 ml of 36% hydrochloric acid and 31 g of tin powder (produced by Wako Pure Chemical Industries, Ltd.) were added and the resulting mixture was stirred under a nitrogen atmosphere at 100C for 4 hours. The resulting solution was added to 800 ml of water, and to this, an aqueous solution of sodium hydroxide was added to adjust a pH to about 10. A precipitation produced was collected by filtration, dissolved in 1000 ml of chloroform, washed with 1000 ml of water, and then dried with magnesium sulfate. The solvent was distilled off from the resulting solution to obtain 21.37 g of compound (10-c).
With iron; acetic acid; at 80℃; for 1h;Inert atmosphere;
In a 250 ml round bottom flask, 4,4-dibromo-2,2-dinitrobenzene (15 mmol) and Fe (0.225 mol) were added to dry acetic acid (100 ml). Under a nitrogen atmosphere, at 80 C After reacting for 1.0 hour, the obtained intermediate mixed solution was directly filtered off the metal residue as the reaction solution for the next reaction.
Microanalysis not done. 3,7-Dicyanodibenzothiophene (14). Anal. Calcd for C14H6N2S.0.25H2O: C, 70.42; H, 2.74; N, 11.73. Found: C, 70.39; H, 2.59; N, 11.51.
40
[ 83834-10-0 ]
[ 91371-12-9 ]
Yield
Reaction Conditions
Operation in experiment
84%
With FeCl3; In 1-methyl-pyrrolidin-2-one; hydrogenchloride;
3,7-Dicyanodibenzothiophene (14). A refluxing solution of 3,7-dibromodibenzothiophene (13, 1.56 g, 4.56 mmol) and copper(I) cyanide (1.27 g, 14.2 mmol) in 1-methyl-2-pyrrolidinone (10 mL) was stirred under nitrogen for 3 h. The cooled reaction mixture was treated with a solution of FeCl3 (3.29 g) in conc. HCl (10 mL). After the initial exotherm, the mixture was stirred with heat for 1 h. The mixture was poured over ice. The resultant gray precipitate was filtered off, dried, and sublimed (280 C., 0.3 mm Hg) to give white powder (0.89 g, 84%): mp >330 C.; 1H NMR (400 MHz, DMSO-d6) delta 8.76 (s, 2 H), 8.71 (d, J=8.2 Hz, 2 H), 8.01 (dd, J=8.2 and 1.4 Hz, 2 H); HPLC (method B)tR 16.84 min (93.5 area %). Anal. (C14H6N2S.0.25H2O) C, H, N.
With sodium methylate; In methanol; N,N-dimethyl-formamide;
2-Methoxy-2'-nitro-4,4'-dibromobiphenyl 15. A solution of sodium methoxide in methanol (22.7 mL, 99.4 mmol) was added dropwise to a solution of <strong>[91371-12-9]4,4'-dibromo-2,2'-dinitrobiphenyl</strong> (14, 33.28 g, 82.79 mmol) in DMF (250 mL) cooled in ice-bath. The reaction mixture was stirred overnight at room temperature under N2. The reaction mixture was then poured into ice-water (700 mL). The precipitated solid was collected and recrystallized from acetonitrile (200 mL) and methanol (100 mL) to give an olive green crystal (18.88 g, 59.0%): mp 127-129 C.; HPLC method 3 tR=9.57 min (96.5 area %); 1H NMR (400 MHz, CDCl3) delta 3.69 (s, 3 H), 7.04 (d, J=1.6 Hz, 1 H), 7.14 (d, J=8.1 Hz, 1 H), 7.23 (dd, J1=1.6 Hz, J2=7.3 Hz, 1 H), 7.26 (d, J=7.3 Hz, 1 H), 7.76 (dd, J1=1.9 Hz, J2=8.1 Hz, 1 H), 8.09 (d, J=1.9 Hz, 1 H); EI-MS m/z 385 (M+). Anal. (C13H9O3NBr2) C, H, N.
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;
2,2 '- dinitro _4,4' - dibromo biphenyl (20g, 49.8mmol), phenoxazine (18.4g, 100.4mmol), palladium acetate (1. 2g, 5 4mmol.), Tri tributylphosphine (1. 6g, 7. 8mmol) and cesium carbonate (48. 6g, 49.4mmol) was dissolved in toluene, under a nitrogen atmosphere, the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred in pentane was added, filtered, purified by silica gel column chromatography, to obtain a solid compound 61-a (16. 0g, 53%).
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;
2, 2 '- dinitro _4, 4' - bis desert biphenyl (. 20. 0g, 49 8mmol), phenothiazines sigh (20. 0g, 100 · 4mmol), palladium acetate (1. 2g, 5. 4mmol), tri-t-butylphosphine (1. 6g, 7. 8mmol) and cesium carbonate (48. 6g, 149. 4mmol) was dissolved in toluene, under a nitrogen atmosphere, the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred in pentane was added, filtered, purified by silica gel column chromatography, to obtain a solid compound 62-a (20. 4g, 64%)
9,9-dimethyl-4a,9,9a,10-tetrahydroacridine[ No CAS ]
[ 91371-12-9 ]
C42H34N4O4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
31%
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;
2,2'-dinitro-4,4'-dibromo-biphenyl (20 (^, dirty 1 49.8), 9,9-dimethyl-acridine (21.08,100 · 4mmol), palladium acetate ( 1 · 2g, 5 · 4mmol), tri-t-butylphosphine (1 · 6g, 7 · 8mmol) and cesium carbonate (48. 6g, 149. 4mmol) was dissolved in toluene, under a nitrogen atmosphere, the reaction was heated at reflux for 8 hours the solvent was evaporated in vacuo, the remaining material was stirred in pentane was added, filtered, purified by silica gel column chromatography, to obtain a solid compound 63-a (10. 2g, 31%)
10,10-dimethyl-5,10-dihydrodibenzo[b,e][1,4]azasiline[ No CAS ]
C40H34N4O4Si2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
36%
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;
2, 2 '- dinitro -4, 4' - dibromo biphenyl (. 20. 0g, 49 8mmol), 10, 10- dimethyl-5, 10-Dihydro-dibenzo [b, e] [1,4] Jie Ya baby miscellaneous Britain (22. 6g, 100. 4mmol), palladium acetate (1. 2g, 5. 4mmol), tri-t-butyl phosphine (1.6g , 7. 8mmol) and cesium carbonate (48. 6g, 149. 4mmol) was dissolved in toluene, under a nitrogen atmosphere, the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred in pentane was added, filtered, purified by silica gel column chromatography, to obtain a solid compound 64-a (12.4g, 36%).
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