* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
[2] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
[3] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
2
[ 51830-50-3 ]
[ 14315-14-1 ]
Reference：
[1] Journal of Organic Chemistry, 1995, vol. 60, # 7, p. 1936 - 1938
[2] Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 96, # 1-4, p. 441 - 444
[3] Patent: US2010/279983, 2010, A1, . Location in patent: Page/Page column 22
3
[ 1505-62-0 ]
[ 14315-14-1 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1950, vol. 566, p. 139,145
[2] Patent: US2004/10004, 2004, A1, . Location in patent: Page 23
4
[ 106-45-6 ]
[ 2032-35-1 ]
[ 14315-14-1 ]
Yield
Reaction Conditions
Operation in experiment
2.77 g
Stage #1: With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 15 h; Stage #2: at 175℃; for 0.75 h;
12116] Step 112117] A mixture of 5.2 g ofbromoacetaldehyde diethylacetal and 10 ml of tetrahydrofuran was added to a mixture of 4.00 g of 4-methylbenzenethiol, 1.4 g of 60percent sodium hydride, and 35 ml of tetrahydroffiran. The reaction mixture was stirred for 15 hours at room temperature. Ten (10) ml of aqueous saturated ammonium chloride solution was added to the reaction mixture, and extraction was performed three times by using tert-butyl methyl ether. The collected organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The residues were added to a mixture of 5 g of diphosphorus pentoxide and lOg ofphosphoric acid that had been stirred for 45 minutes at 175° C., and the residue was stirred for 5 minutes. The reaction mixture was poured into ice water, and extraction was performed three times by using tert-butyl methyl ethet The collected organic layer was washed with water and saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The residues were subjected to silica gel colunm chromatography, thereby obtaining 2.77 g of 5-methylbenzo[b] thiophene
Reference：
[1] Journal of Heterocyclic Chemistry, 1988, vol. 25, p. 1271 - 1272
[2] Proceedings - Indian Academy of Sciences, Section A, 1950, # 32, p. 396,401
[3] Journal of Medicinal Chemistry, 2011, vol. 54, # 5, p. 1244 - 1255
6
[ 6007-83-6 ]
[ 542-92-7 ]
[ 16587-47-6 ]
[ 14315-14-1 ]
[ 14315-15-2 ]
[ 14315-11-8 ]
Reference：
[1] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
[2] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
[3] Journal of the American Chemical Society, 1981, vol. 103, # 10, p. 2760 - 2769
7
[ 1199-06-0 ]
[ 14315-14-1 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 14, p. 3608 - 3612
8
[ 56639-88-4 ]
[ 14315-14-1 ]
Reference：
[1] Journal of the American Chemical Society, 1945, vol. 67, p. 1643
9
[ 106-45-6 ]
[ 14315-14-1 ]
Reference：
[1] Journal of Medicinal Chemistry, 2011, vol. 54, # 5, p. 1244 - 1255
10
[ 106-43-4 ]
[ 74-86-2 ]
[ 14315-14-1 ]
[ 120-12-7 ]
[ 108-88-3 ]
[ 95-15-8 ]
Reference：
[1] Russian Journal of Organic Chemistry, 1993, vol. 29, # 11.2, p. 1863 - 1867[2] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 11, p. 2246 - 2250
11
[ 65520-23-2 ]
[ 14315-14-1 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1915, vol. 408, p. 281
12
[ 106-45-6 ]
[ 74-86-2 ]
[ 14315-14-1 ]
Reference：
[1] Journal of the Institute of Polytechnics, Osaka City University, Series C: Chemistry, 1950, vol. <C> 1, # 2, p. 31[2] Nippon Kagaku Zasshi, 1952, vol. 73, p. 246
[3] Journal of the Institute of Polytechnics, Osaka City University, Series C: Chemistry, 1950, vol. <C> 1, # 2, p. 31[4] Nippon Kagaku Zasshi, 1952, vol. 73, p. 246
13
[ 13616-73-4 ]
[ 14315-14-1 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1950, vol. 566, p. 139,145
14
[ 103-19-5 ]
[ 74-86-2 ]
[ 14315-14-1 ]
Reference：
[1] Journal of the Institute of Polytechnics, Osaka City University, Series C: Chemistry, 1950, vol. <C> 1, # 2, p. 31[2] Nippon Kagaku Zasshi, 1952, vol. 73, p. 246
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 3h;Heating / reflux;
5-Methylbenzo (b) thiophene (0.37g, 2. 48mmol) is dissolved in carbon tetrachloride (4ml) and treated with N-bromosuccinimide (0.46g, 2. 58mmol) and 2,2'-azobis-isobutyronitrile (lOmg). The mixture is stirred and warmed under reflux for 3h and then left to cool to room temperature overnight. The mixture is filtered and the filtrate evaporated to dryness in vacuum at 40C. The residual brown oil is treated with iso-hexane and warmed until it dissolves, before leaving to cool. The mixture is chilled and scratched until crystalline solid forms. The temperature is allowed to warm back up to room temperature and then the solid is isolated by filtration. The solid is then washed with more iso-hexane. The filtrate is concentrated to half the volume and then chilled again with scratching. Solid is re-formed and isolated by filtration, and air drying. The desired product is formed as a white solid, this material is used as'seed'crystals. The procedure is then repeated on a larger scale. Thus 5-methylbenzo (b) thiophene (51.3g, 0. 35mol) is dissolved in carbon tetrachloride (540ml), N-Bromosuccinimide (63.8g, 0. 36mol, 1.04eq), 2,2'-azobis-isobutyronitrile (0.4g) are then added. The crude product is crystallised from iso-hexane (no heating) using'seed'crystals. The material immediately formed and is isolated by filtration and dried. This material is dried further in vacuo at room temperature to give the desired product (69.62g) which is recrystallised from hot iso-hexane and left to cool. The solid is isolated by filtration and dried in vacuo at room temperature to give the required product (59.6g, 76%) ; 1H NMR (300 MHz, CDC13) : 8= 7. 88-7. 81 (2 H, m), 7.50-7. 45 (1 H, m), 7.41-7. 35 (1 H, m), 7.34-7. 30 (1 H, m) and 4.65 (2 H, s).
41%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 3h;Reflux;
5-Methylbenzo[b]thiophene (500 mg, 3.37 mmol), 108 N-bromosuccinimide (560 mg, 3.37 mmol) and 109 AIBN (28 mg, 0.05 mmol) were dissolved in 110 carbon tetrachloride (45 mL). The reaction mixture was refluxed for 3 hours. The reaction mixture was cooled, and the suspension was filtered. The filtrate was concentrated under reduced pressure. The resulting residue was purified on an ISCO chromatography (100% hexane) to give the 114 product as a white solid (312 mg, 41%); 1H NMR (300 MHz) (CDCl3) delta 7.87-7.85 (m, 2H), 7.48 (d, J=6 Hz, 1H), 7.39 (dd, J=8 Hz, J=2 Hz, 1H), 7.32 (dd, J=6 Hz, 1H), 4.66 (s, 2H).
With N-Bromosuccinimide;
5-Bromomethylbenzo[b]thiophene was prepared from 5-methylbenzo[b]thiophene and N-bromosuccinimide as in Example 6 except that the reaction was refluxed 15 hours. The title compound was prepared as in example 7 from the corresponding beta-keto ester and anhydrous hydrazine.
With N-Bromosuccinimide;
5-Bromomethylbenzo[b]thiophene was prepared from 5-methylbenzo[b]thiophene and N-bromosuccinimide as in Example 1 except that the reaction was refluxed 15 hours. The title compound was prepared as in example 1 from the corresponding beta-keto ester and anhydrous hydrazine.
With N-Bromosuccinimide; dibenzoyl peroxide;
EXAMPLE 123 N-?5-[(R)-1-(Hydroxy-2-[[1-(benzo[b]thiophen-5-yl)-2-phenylethyl]amino]ethyl)-2-hydroxyphenyl]methanesulfonamide, trifluoroacetate salt STR176 A. 5-Benzo[b]thiophenylcarboxaldehyde A mixture of 5-methylbenzo[b]thiophene (3.8 g, 25.6 mmol), NBS (4.7 g, 27 mmol), and benzoyl peroxide (310 mg, 1.3 mmol) were refluxed one hour in CCl4 (100 mL) while being irradiated with a sunlamp. Upon completion, the reaction was cooled, diluted with Et2 O, filtered and concentrated to yield 5.8 g of 5-bromomethylbenzo[b]thiophene.
With N-Bromosuccinimide; In tetrachloromethane; for 4h;Heating / reflux;
A solution containing 5-methylbenzo[b]thiophene (37 g), N-bromosuccinimide (46 g), and tetrachloromethane (400 ml) was refluxed for 4 h, cooled, and filtered. The filtrate was evaporated and the resultant residue crystallised from hexane to give the subtitle compound (40 g).
With N-Bromosuccinimide; 1,1'-azobis(1-cyanocyclohexanenitrile); In tetrachloromethane; for 6h;Inert atmosphere; Reflux;
Preparative Example 485-(BROMOMETHYL)-1-BENZOTHIOPHENEN-Bromosuccinimide (4.53 g, 25.4 mmol, 1.20 eq) and 1,1'-azobis(cyclohexane-carbonitrile) (260 mg, 1.06 mmol, 0.05 eq) were added to a solution of 5-methyl-1-benzothiophene (3.14 g, 21.2 mmol, 1 eq) in carbon tetrachloride (90 mL) under nitrogen. The reaction mixture was heated under reflux and after 3 h a further amount of 1,1'-azobis(cyclohexane-carbonitrile) (260 mg, 1.06 mmol, 0.05 eq) was added. After an additional 3 h of heating under reflux, the reaction mixture was cooled down to room temperature and filtered. The filtrate was transferred to a separatory funnel, washed with a saturated aqueous solution of sodium bicarbonate, and the organic phase was dried over sodium sulfate, filtered and concentrated. Purification by flash chromatography on silica gel (ethyl acetate/hexane, 2:98 to 4:96) afforded 5-(bromomethyl)-1-benzothiophene.
With N-Bromosuccinimide; In ethyl acetate; at 30℃; for 0.0333333h;Flow reactor; Irradiation;
A solution of 1.1 g of 5-methyl-1-benzothiophene (Compound B) in 3.3 mL of ethyl acetate was prepared (solution I). Separately, a solution of 0.66 g of NBS in 25 mL of ethyl acetate was prepared (solution II). The solutions I and II were each fed by a syringe pump to an in-line mixer connected to a FEP tube having an inner diameter of 0.5 mm, where the flow rates of the solutions I and II were adjusted so that the amount of NBS was 1.1 equivalents based on that of Compound B. After mixing the solutions I and II in the in-line mixer, the FEP tube was irradiated with a high pressure mercury lamp (UM-102, manufactured by Ushio Inc.). The average residence time the solution takes to pass through the section irradiated with the high-pressure mercury lamp was set to 2 minutes. Further, the in-line mixer and a high pressure mercury lamp wrapped with the reaction tube were immersed in a water bath and the water temperature was held at 30 C. The obtained reaction solution was measured by HPLC, and it was determined that the peak area ratio of Compound A was 90%. The peak area ratios of Compounds B, C and D are shown in Table 2.
With N-Bromosuccinimide; In tetrachloromethane; n-heptane; ethyl acetate;
Step 1 5-Bromomethylbenzo[b]thiophene A mixture of 5-methylbenzo[b]thiophene (5.0 g, 33.7 mmol), N-bromosuccinimide (5.7 g, 32.0 mmol) and dibenzoylperoxide (0.25 g, 1.01 mmol) in tetrachloromethane was heated to reflux for 2 hours. It was cooled to room temperature and left for 16 hours. The solid was filtered off. The solvent was removed in vacuo. The crude product was purified by flash chromatography on silica (300 g), using ethyl acetate/heptane (1:10) as eluent, to give 6.37 g (83%) of 5-bromomethylbenzo[b]thiophene. 1H NMR (CDCl3): delta4.60 (s, 2 H), 7.28 (d, 1 H), 7.35 (d, 1 H), 7.45 (d, 1 H), 7.70 (m, 2 H).
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In benzene; at 75 - 80℃; for 0.5h;
To a mixture of 2.04 g of NBS and 22 mg of 2,2?-azobis (2-methylpropionitrile) in 15 mL of benzene, a solution of 1.00 g of 5-methyl-1-benzothiophene and 22 mg of 2,2?-azobis(2-methylpropionitrile) in 9 mL of benzene was added dropwise at 80 C. over 30 minutes, and the resulting mixture was stirred for 30 minutes at the same temperature. The obtained reaction solution was measured by HPLC, and it was determined that the peak area ratio of Compound A was 60%. The peak area ratios of Compounds B, C and D are shown in Table 1.
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