Month: November 2020

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

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

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

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

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

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

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

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

61921-39-9, A common compound: 61921-39-9, name is 4-Bromotetraphene, belongs to bromides-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below.

Example 54 Synthesis of 4-(diphenylamino)benz[a]anthracene 190 mul (1 mmol) of chlorodi-tert-butylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to a suspension of 15.4 g (50 mmol) of 4-bromobenz[a]anthracene, 10.2 g (60 mmol) of diphenylamine and 7.7 g (80 mmol) of sodium tert-butoxide in 500 ml of toluene, and the mixture is subsequently heated under reflux for 5 h. After the mixture has been cooled to 60 C., 500 ml of water are added, the organic phase is separated off, filtered through silica gel, evaporated virtually to dryness at 80 C. in vacuo, and 300 ml of ethanol are then added. After cooling, the solid is filtered off with suction. Recrystallisation five times from dioxane (about 8 ml/g); sublimation (p=5*10-5 mbar, T=280 C.). Yield: 12.7 g (32 mmol), 64.1%, purity 99.9% (HPLC), Tg=74.7 C.

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, 4-Bromotetraphene, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Stoessel, Philipp; Buesing, Arne; Heil, Holger; US2010/187505; (2010); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

699-03-6, A common heterocyclic compound, 699-03-6, name is 1-(4-Bromophenyl)-N-methylmethanamine, molecular formula is C8H10BrN, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

A solution of 4-bromo-N-methylbenzylamine (199 mg,1.00 mmol), 3-pyridylboroxine (163 mg, 0.518 mmol), sodium carbonate (2 M, 4mL) and tetrakis(triphenylphosphine)-palladium(0) (30 mg, 0.026 mmol) in 1,4-dioxane (50 mL) was refluxed for 18 h. The solvent was eliminated under reduced pressure and the crude material was dissolved in a mixture of CH2Cl2 and CH3OH (1:1, 10 mL) and filtered through celite. After evaporation of the solvent, the crude material was purified by flash column chromatography (hexanes: ethyl acetate 6:4 and 1 % NEt3) to afford 1 as yellow oil (165 mg, 83 %); 1HNMR (CD2Cl2, 500 MHz): delta = 8.83 ppm (dd, J = 2.4 and 0.7 Hz, 1H), 8.54 (dd, J = 4.8 and 1.6 Hz, 1H), 7.89 (ddd, J = 7.9, 2.3 and 1.7 Hz, 1H), 7.58-7.56(m, 2H), 7.45-7.43 (m, 2H), 7.35 (ddd, J= 7.9, 4.8 Hz and 0.8 Hz, 1H), 3.78 (s, 2H), 2.43 (s, 3H), 1.64 (s, 1H); 13CNMR (125 MHz, CD2Cl2): delta = 148.9 ppm, 148.8 141.2, 137.0,136.9, 134.6, 129.4, 127.5, 124.1, 56.1, 36.3; IR (NaCl): nu = 3300 cm-1, 3028, 2933, 2844,2790, 2360, 1918, 1684, 1653, 1577, 1559, 1517, 1474, 1429, 1396, 1354, 1188,1129, 1103, 1024, 1001, 848, 796, 711; MS (CI, CH5+): m/z (%) = 199 (100) [M+H]+,168 (20), MS (EI, 70 eV): m/z (%):198 (100) [M]+, 168 (66), 156 (40); HR-MS (EI, 70 eV): m/z =198.11338 [M]+: calcd for C13H14N2:198.11570.

The synthetic route of 699-03-6 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Keller, Marco; Wolfgardt, Annette; Mueller, Christoph; Wilcken, Rainer; Boeckler, Frank M.; Oliaro-Bosso, Simonetta; Ferrante, Terenzio; Balliano, Gianni; Bracher, Franz; European Journal of Medicinal Chemistry; vol. 109; (2016); p. 13 – 22;,
Bromide – Wikipedia,
bromide – Wiktionary