Category: bromides-buliding-blocks

1559-88-2, In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 1559-88-2 as follows.

A solution of 1-bromo- 2,3,5,6-tetrafluorobenzene (4.58 g, 20 mmol) in 100 mL of anhydrous THF was cooled to -100 C (liquid nitrogen/ EtOH) under nitrogen. Then 1.4M solution of sec-BuLi in cyclohexane (15 mL, 21 mmol) was added dropwise at -100 C to -90 C. The mixture was stirred at -100 C to -90 C for 10 min, then a solution of R-(+)-propylene oxide (1.51 g, 1.8 mL, 26 mmol) in 15 mL of THF was added dropwise at -100 C to -90 C, then the mixture was cooled to -105 C and a 46.5% solution Of BF3 in diethyl ether (4.18 mL, 30 mmol) was added dropwise. The mixture was stirred at -100 C to -90 C for 2 h, then the reaction was quenched with 20 mL of sat. aq. NH4Cl at -90 C. The mixture was stirred and warmed to 0 C overnight. Then 20 mL of water was added and mixture was extracted with EtOAc (2×60 mL), the extract was dried over Na2SO4 and evaporated to give crude oil, which was purified by column (silicagel, EtOAc/hexane 1 :9, Rf = 0.57 in EtOAc/hexane 3:7) to give (2R)-1-(2,3,5,6-tetrafluorophenyl)propan-2- ol (2.57 g, 62 %) as a white solid. 1H NMR (300 MHz, CDCl3): delta 6.96 (m, 1H), 4.1 1 (m, 1H), 2.89 (m, 2H), 1.47 (d, J = 5.46 Hz, 1H), 1.29 (d, J = 6.21 Hz, 3H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1559-88-2, and friends who are interested can also refer to it.

Reference:
Patent; CHEMBRIDGE CORPORATION; WO2009/117097; (2009); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

49764-63-8, Adding a certain compound to certain chemical reactions, such as: 49764-63-8, name is 4,5-Dibromobenzene-1,2-diamine, belongs to bromides-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 49764-63-8.

General procedure: Intermediate1 (3.17 g, 8.7 mmol) and 4,5-dibromobenzene-1,2-diamine (3.02 g, 11.35 mmol) were dissolved in 90 mL acetic acid,and then heated to reflux for 16 h. After cooling down, the resultingmixture was poured into water and neutralized by sodium hydroxide.The suspension was extracted with chloroform(50 mL 3), and the combined organic layer was washed withwater and dried over anhydrous sodium sulfate. After that, thesolvent was removed by vacuum distillation and the rest solid waspurified with a silica gel column. Using dichloromethane/methanol(v/v) 20:1 as eluent and gave the target compound as light yellowsolid (4.3 g, yield: 83%).

According to the analysis of related databases, 49764-63-8, the application of this compound in the production field has become more and more popular.

Reference:
Article; Yin, Xiaojun; Sun, Hengda; Zeng, Weixuan; Xiang, Yepeng; Zhou, Tao; Ma, Dongge; Yang, Chuluo; Organic electronics; vol. 37; (2016); p. 439 – 447;,
Bromide – Wikipedia,
bromide – Wiktionary

3814-30-0, Adding a certain compound to certain chemical reactions, such as: 3814-30-0, name is (Bromomethyl)cyclopentane, belongs to bromides-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 3814-30-0.

39) N-(3-(cyclopentylmethoxy)-2-methoxybenzyl)-3-cyclopropyl-1-methyl-1H-pyrazole-5-carboxamide To a solution of aldehyde (10.0 g, 65.79 mmol, 1.0 eq) in toluene (100 mL) was added 2,4-dimethoxybenzyl amine (10.89 g, 65.79 mmol, 1.0 eq) and the reaction mixture was stirred at room temperature for 24 h. Toluene was removed to give a residue, which was taken in MeOH (100 mL) and then NaBH4 (4.97 g, 131.58 mmol, 2.0 eq) was added slowly. The reaction mixture was stirred at room temperature for 6 h. Solvent was removed and the residue was extracted in Ethyl acetate and stirred with saturated aq NaHCO3 for 1 h. The organic layer was collected, dried and solvent was removed to give the crude amine, which was used in the next step without further purification. To a solution of the crude amine (7.26 mmol, 1.0 eq) in DMF (20 mL) was added the acid (1.21 g, 7.26 mmol, 1.0 eq), DIEA (4.68 g, 36.30 mmol, 5 eq) and HBTU (3.30 g, 8.71 mmol, 1.2 eq) and the reaction mixture was stirred at rt for 12 h. The reaction mixture was then diluted with ethyl acetate (100 mL) and washed with 10% aq HCl (1*50 mL), sat NaHCO3 (1*50 mL) and water (4*50 mL). Organic layer was collected, dried (MgSO4) and evaporated to give a crude product, which was taken in 150 mL of methanol and NaOH (290 mg, 7.26 mmol, 1.0 eq) was added and stirred at room temperature for 24 h. Methanol was removed and the residue was neutralized with 10% aq HCl. The reaction mixture was then extracted with ethyl acetate (2*). Organic layer was collected, dried (MgSO4) and evaporated to give a crude product, which was purified by column chromatography (EtOAc/Hexane) to give the amide. To a solution of the hydroxy amide (500 mg, 1.07 mmol, 1.0 eq) in DMF (15 mL) was added Cs2CO3 (1.04 g, 3.21 mmol, 3.0 eq) and stirred at room temperature for 20 min. Then bromide (261 mg, 1.60 mmol, 1.5 eq) was added and stirred at rt for 24 h. The reaction mixture was then diluted with ethyl acetate (25 mL) and washed with water (4*). Organic layer was collected, dried (MgSO4) and evaporated to give a residue, which was then treated with 95% TFA:H2O for 12 h. TFA was removed and azeotroped with toluene to give a residue, which was purified by column chromatography (EtOAc/Hexane 10% to 50%) to give the desired product. Mass Spectrum (LCMS, ESI Pos.) Calcd. For C12H30N2O3: 384.0 (M+H), Found 362.0.

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, (Bromomethyl)cyclopentane, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Prosetta Antiviral ,Inc.; Selvarajah, Suganya; Paulvannan, Kumar; (58 pag.)US2018/118679; (2018); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

627871-16-3, The chemical industry reduces the impact on the environment during synthesis 627871-16-3, name is 5-Bromo-4-fluoro-2-methylaniline, I believe this compound will play a more active role in future production and life.

To a suspension [OF 5-BROMO-4-FLUORO-2-METHYLANILINE (11.] 2 g, 54.9 mmol) in concentrated [HCL] (35 mL) was added dropwise a solution of sodium nitrite (4.17 g, 60.4 mmol) in water (20 mL) over 30 minutes at [0C.] To the mixture was added dropwise a solution [OF SNCI2*2H2O] (37.2 g, 165 mmol) in concentrated HCl (45 mL) over 1 hour. After stirring for 2 hours at 0 [C,] the reaction mixture was basified with 50% NaOH (50 mL). The mixture was further diluted with water (50 mL) and treated with another 50% NaOH (20 mL) and then crushed ice (200 g). The reaction mixture was extracted with ether (3 x 200 mL) and the combined organic phases were washed with brine, dried over [NA2SO4,] and filtered. The filtrate was acidified by adding an anhydrous solution of [HCL] in ether (2 N in ether, 42 mL, 82.5 mmol). The precipitate was collected and dried under reduced pressure to give 9.92 g [(71 %)] of title compound as a pale yellow [SOLID.’H] NMR (DMSO): 300 MHz [6] 10.18 (bs, 3H), 7.98 (bs, 1H), 7.21 (m, 2H), 2.16 (s, 3H).

The chemical industry reduces the impact on the environment during synthesis 5-Bromo-4-fluoro-2-methylaniline. I believe this compound will play a more active role in future production and life.

Reference:
Patent; WYETH; VIROPHARMA INCORPORATED; WO2003/99824; (2003); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 937046-98-5 as follows. 937046-98-5

To a suspension of the bromide 3 (prepared according to W02009/132135) (710 mg, 3.33 mmol) in dry THF (6.0 mE) was added 1,2-bis(chlorodimethylsilyl)ethane (717 mg, 3.33 mmol) in one portion at room temperature. Afier 1 h, the resulting slurry was cooled to -78 C. and n-l3uEi (7.5 mE of a 1.6M solution in hexanes, 12.0 mmol) was added dropwise over a 5 mm period. After stirring for 20 min at this temperature, a solution of 4 (1.0 g, 3.03 mmol) in dry THF (2.85 mE) was added dropwise over several minutes. The reaction was stirred at this temperature for 3 h and then allowed to warm to 0 C. Glacial HOAc (2.5 mE) was added and the reaction was warmed to room temperature. After vigorously stirring for 10 mm, the bulk of the solvents were removed under reduced pressure and the reaction mixture was partitioned between ethyl acetate and watet The layers were separated and the organic layer was washed with sat. NaHCO3, brine, dried over Na2504 and concentrated to provide a dark brown residue. Purification of the residue by flash column chromatography on silica gel using a gradient of 50% hexanes in ethyl acetate to 20% hexanes in ethyl acetate provided the desired product 5 (591 mg, 42%) as a pale yellow foam.

According to the analysis of related databases, 937046-98-5, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Gilead Sciences, Inc.; Clarke, Michael O’ Neil Hanrahan; Kim, Choung U.; Lew, Willard; (51 pag.)US2017/226140; (2017); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Adding a certain compound to certain chemical reactions, such as: 937046-98-5, name is 7-Bromopyrrolo[2,1-f][1,2,4]triazin-4-amine, belongs to bromides-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 937046-98-5, 937046-98-5

A mixture of 7-bromopyrrolo[2,1-f][1,2,4]triazin-4-amine (0.200 g, 0.939 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid (0.279 g, 1.127 mmol), tripotassium phosphate (2 M in water) (1.408 mL, 2.82 mmol), and N,N- dimethylformamide (4.0 mL) was degassed with vacuum and nitrogen (3x).1,1′-Bis(di- tert-butylphosphino)ferrocene palladium dichloride (0.069 g, 0.094 mmol) was added, and the reaction mixture was degassed (2x). The reaction mixture was immediately immersed in an oil bath at 95 C and stirred overnight. The reaction mixture was cooled to rt and then diluted with water (2 mL) followed by 1N aqueous hydrochloric acid (2 mL), resulting in a precipitate. The solid was collected by vacuum filtration and dried under reduced pressure to give 3-(4-aminopyrrolo[2,1-f][1,2,4]triazin-7-yl)benzoic acid (0.117 g, 0.460 mmol, 49.0 % yield) as a gray solid. (0980) MS ESI m/z 255.1 (M+H)

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, 7-Bromopyrrolo[2,1-f][1,2,4]triazin-4-amine, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; WATTERSON, Scott Hunter; ANDAPPAN MURUGAIAH SUBBAIAH, Murugaiah; DZIERBA, Carolyn Diane; GONG, Hua; GUERNON, Jason M.; GUO, Junqing; HART, Amy C.; LUO, Guanglin; MACOR, John E.; PITTS, William J.; SHI, Jianliang; VENABLES, Brian Lee; WEIGELT, Carolyn A.; WU, Yong-Jin; ZHENG, Zhizhen Barbara; SIT, Sing-Yuen; CHEN, Jie; (810 pag.)WO2019/147782; (2019); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 22385-77-9 name is 1-Bromo-3,5-di-tert-butylbenzene, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below. 22385-77-9

A solution of 2,2,6,6-tetramethylpiperidine (2.0 mL, 12 mmol) in THF (12 mL) was treated with n-BuLi (7.5mL, 1.60 M in hexane, 12 mmol) at 0 ¡ãC. After stirring for 1 h at 0 ¡ãC the solution wasadded to a solution of bromoferrocene (1.32 g, 5.00 mmol) in THF (10 mL) at ?78 ¡ãC.After stirring for 30 min at ?78 ¡ãC and 3 h at ?30 ¡ãC the reaction mixture wastransferred to a suspension of ZnCl2 (1.36 g, 10.0 mmol) in THF (10 mL) at ?78 ¡ãC.Stirring was continued at ?78 ¡ãC for 30 min before the mixture was warmed to roomtemperature, where stirring was maintained for 30 min. To the resulting solution wasadded a solution of 1-bromo-3,5-di-t-butylbenzene (1.48 g, 5.50 mmol) and [Pd(PPh3)4](0.29 g, 0.25 mmol) in THF (10 mL). The reaction mixture was heated to 60 ¡ãC for 10hours, before the reaction was quenched with a saturated aqueous ammonium chloridesolution. The reaction mixture was extracted with hexane and the combined organicphases were washed with water and dried over MgSO4. After filtration, the filtrate wasevaporated to dryness under reduced pressure and the obtained residue was purified bycolumn chromatography on silica gel (hexane) to give compound 3 (2.01 g, 4.43 mmol,89percent). 3: orange solid; m.p. 87?89 ¡ãC; 1H NMR (300 MHz, CDCl3) delta 1.37 (s, 18H), 4.17(s, 5H), 4.22 (t, J = 2.6 Hz, 1H), 4.43 (dd, J = 2.6, 1.4 Hz), 4.54 (dd, J = 2.6, 1.4 Hz),7.33 (t, J = 1.8 Hz, 1H), 7.55 (d, J = 1.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) delta 31.6 (q),34.8 (q), 66.3 (d), 67.5 (d), 71.0 (d), 72.0 (d), 78.3 (s), 87.7 (s), 120.8 (d), 123.9 (d),135.2 (s), 149.8 (s). Anal. Calcd for C24H29BrFe: C, 63.60; H, 6.45percent. Found: C, 63.84;H, 6.48percent.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 22385-77-9, and friends who are interested can also refer to it.

Reference:
Article; Sasamori, Takahiro; Suzuki, Yuko; Sakagami, Michiyasu; Miyake, Hideaki; Tokitoh, Norihiro; Chemistry Letters; vol. 43; 9; (2014); p. 1464 – 1466;,
Bromide – Wikipedia,
bromide – Wiktionary

51554-93-9, name is 1-Bromo-4-octylbenzene, belongs to bromides-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. 51554-93-9

Pd(OAc)2 (0.232 mg, 1.032 mumol), and S-Phos (0.424 mg, 1.032 mumol) were added to a suspension of K2CO3 (35.7 mg, 0.258 mmol), 1-bromo-4-octylbenzene (0.012 ml, 0.052 mmol), 5′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-[1,2′-bipyridin]-2-one (20 mg, 0.067 mmol) in acetonitrile/water (1.5:1). The suspension was degassed for 5 minutes and refluxed for 6 h. The reaction mixture was extracted with EtOAc, washed with brine, dried with MgSO4 and filtered. After evaporation of the organic solvent under reduced pressure, the resulting residue was purified by column chromatography over silica gel (100% hexanes to 40/60 hexanes/EtOAc) to provide the title compound as an off-white solid (81% yield). 1H NMR (400 MHz, CDCl3) delta 8.75 (t, J = 1.7 Hz, 1H), 8.00 (d, J = 1.6 Hz, 3H), 7.92 (dd, J = 2.1 Hz, 7.1 Hz, 1H), 7.52 (d, J = 8.3 Hz, 2H), 7.41 (m, 1H), 7.31 (d, J = 8.3 Hz, 2H), 6.71-6.63 (m, 1H), 6.36-6.27 (m, 1H), 2.66 (t, J = 7.8 Hz, 2H), 1.71-1.59 (m, 2H), 1.37-1.22 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) delta 162.3, 150.5, 147.0, 143.5, 140.2, 136.3, 136.0, 135.9, 134.1, 129.3, 127.0, 122.1, 121.1, 106.3, 35.7, 31.9, 31.5, 29.5, 29.4, 29.3, 29.2, 22.7, 14.1; HRMS (ESI+) m/z calcd for C24H28N2O [M+Na]+ 383.2094, found 383.2113.

Statistics shows that 51554-93-9 is playing an increasingly important role. we look forward to future research findings about 1-Bromo-4-octylbenzene.

Reference:
Article; Raje, Mithun R.; Knott, Kenneth; Kharel, Yugesh; Bissel, Philippe; Lynch, Kevin R.; Santos, Webster L.; Bioorganic and Medicinal Chemistry; vol. 20; 1; (2012); p. 183 – 194;,
Bromide – Wikipedia,
bromide – Wiktionary

61326-44-1, Name is 1,1,2,2-Tetrakis(4-bromophenyl)ethene, 61326-44-1, belongs to bromides-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows.

General procedure: The synthesis of intermediate tetra-brominated TPE has been reported in previous literatureS1. The solid reactant 2 (100 mg, 0.15 mmol) and solid reactant 3 (0.9 mmol), catalyst palladium acetate (1.73 mg, 0.0077 mmol) and triphenylphosphine (4.04 mg, 0.0154 mmol) was added into the cube which was pumped three times, then anhydrous and anaerobic DMF (5 ml) and bubbled triethylamine(1 ml) was injected. After quickly switching the stopper, the reaction system would flux for two days. When completed, the reaction was cooled to room temperature, then poured into a large amount of water and extracted three times with dichloromethane, and finally washed with saturated saline multiple times to obtain the organic phase. After the organic phase was dried over anhydrous sodium sulfate, the dichloromethane was swirled off by rotary evaporation. TPE-Py was purified by silica gel column chromatography (petroleum ether : ethyl acetate = 1:5) to obtain the solid yellow powder, otherwise TPE-Ph was eluted by petroleum ether/dichloromethane (1:2) to acquire the orange powder.

Statistics shows that 1,1,2,2-Tetrakis(4-bromophenyl)ethene is playing an increasingly important role. we look forward to future research findings about 61326-44-1.

Reference:
Article; Ma, Xiaoxie; Hu, Linli; Han, Xie; Yin, Jun; Chinese Chemical Letters; vol. 29; 10; (2018); p. 1489 – 1492;,
Bromide – Wikipedia,
bromide – Wiktionary

67567-26-4, name is 4-Bromo-2,6-difluoroaniline, belongs to bromides-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. 67567-26-4

4-Bromo-2,6-difluoro-phenylamine (200 g, 0.961 mol) and N-isopropyl acetamide (107 g, 1.057 mol) in toluene (1000 mL) were stirring at 10-15 C. Phosphoryl chloride (177 g, 1.154 mol) and triethylamine (117 g, 1.156 moles) were slowly added. The reaction mixture was heated to reflux for 2-3 hours. The reaction mass was cooled to 10-15 C and water was slowly added into the reaction mixture which was stirred at 30-35 C for 15-20 minutes. The pH of the reaction mass was adjusted to 7.5-8.0 with a sodium hydroxide solution, stirred for 30 minutes at 30-35 C, and the layers were separated. The organic layer was washed with water and the layers were againseparated. Potassium hydroxide (161.5 g, 2.88 mol) and dimethylsulfoxide 400 mL at 30-35 Cwere charged to the organic layer. The reaction mixture was heated to reflux and water wasadded azeotropically for 2-4 hours at reflux temperature. The reaction mass was cooled to 25-30C and water was slowly added into the reaction mixture. The reaction mixture was stirred at 30-35 C for 15-20 minutes and the layers were separated. The organic layer was washed with anaqueous sodium chloride solution. The organic layer was concentrated under vacuum. Toluene (160 mL) and hexanes (1000 mL) were charged to the residue and the resulting mixture was stirred for 2-3 hours at room temperature. The mixture was filtered and the collected solid was washed with hexanes and dried at 50-55 C to yield 215 g (82.3%) of 6-bromo-4-fluoro-1- isopropyl-2-methyl-1H-benzoimidazole with a purity of 99.70%.

Statistics shows that 67567-26-4 is playing an increasingly important role. we look forward to future research findings about 4-Bromo-2,6-difluoroaniline.

Reference:
Patent; MYLAN LABORATORIES LIMITED; JETTI, Ramakoteswara Rao; INDUKURI, Anjaneyaraju; BOMMAREDDY, Aggi Ramireddy; SRINIVASARAO, Attanti Veera Venkata; JEBARAJ, Rathinapandian; CHANDUPATLA, Shivakumar; BATHARAJU, Ramesh; KUNAMNENI, Sunil; (74 pag.)WO2019/102492; (2019); A1;,
Bromide – Wikipedia,
bromide – Wiktionary