Category: bromides-buliding-blocks

Some common heterocyclic compound, 327-51-5, name is 1,4-Dibromo-2,5-difluorobenzene, molecular formula is C6H2Br2F2, 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. category: bromides-buliding-blocks

A solution of 1,4-dibromo-2,5-difluorobenzene (640 mg, 2.35 mmol) in dry diethyl ether (10 mL) cooled in a dry ice-acetone bath was treated dropwise with 2.5 M n-butyllithium in hexanes (1.04 mL, 2.59 mmol). The resulting solution was stirred at -78 C. for 30 min, then was treated with a piece of dry ice. The cooling bath was removed after 5 min and the mixture was stirred for another 30 min while warming to room temperature. The mixture was diluted with EtOAc and water. The organic phase was separated and washed twice with saturated aqueous NaHCO3. The combined aqueous phases were acidified with 1 M aqueous HCl, extracted twice with DCM, and the combined organic phases were dried and concentrated to give 4-bromo-2,5-difluorobenzoic acid as a white solid (297 mg, 53% yield).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 327-51-5, its application will become more common.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; Liu, Qingjie; Watterson, Scott Hunter; Batt, Douglas G.; Ahmad, Saleem; Beaudoin Bertrand, Myra; Gong, Hua; Guo, Weiwei; Macor, John E.; Ngu, Khehyong; Tebben, Andrew J.; Tino, Joseph A.; (177 pag.)US2016/115126; (2016); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 201138-91-2, Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 201138-91-2, name is 4,6-Dibromodibenzo[b,d]furan, This compound has unique chemical properties. The synthetic route is as follows.

0.1 mol of 4,6-dibromodibenzofuran was dissolved in 320 ml of 1,4-dioxane solvent.Stirring with nitrogen,Add 0.09 mol of [4-(triphenylsilyl)phenyl]boronic acid,0.25 mol of potassium carbonate,0.0001 mol of tetrakis(triphenylphosphine)palladium,Warming up to reflux reaction,After 5 hours, the basic reaction of the raw materials was determined by HPLC.The reaction solution was dried under reduced pressure.The residue was subjected to column chromatography to give Intermediate 1-9-1. (Yield: 63%)

The chemical industry reduces the impact on the environment during synthesis 4,6-Dibromodibenzo[b,d]furan. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Beijing Lv Ren Science And Technology Co., Ltd.; Lv Yao; Jia Xueyi; (19 pag.)CN108424420; (2018); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 59907-13-0, These common heterocyclic compound, 59907-13-0, name is 2-Bromo-1-fluoro-3-methylbenzene, 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 10 mL round-bottomed flask was charged with 2-bromo-l-fluoro-3- methylbenzene (0.13 mL, 0.70 mmol, Sigma-Aldrich, St. Louis, MO) and tetrahydrofuran (2.0 mL). The solution was cooled to -78 C, n-butyllithium (0.28 mL of a 2.5 M solution with hexane, 0.70 mmol, Sigma-Aldrich, St. Louis, MO) was added, and then the reaction mixture was stirred for 30 min. After that time, a solution of N-(l-benzofuran-2-ylmethylidene)-3,4-dihydro-2H-l,5- benzodioxepine-7-sulfonamide (intermediate A) (0.10 g, 0.28 mmol) and tetrahydrofuran (3.0 mL) was added. After stirring for 1 h, water (0.10 mL) was added, and the reaction mixture was warmed to room temperature andconcentrated. The residue was subjected to reversed-phase preparative HPLC (Phenomenex Gemini CI 8 column (Phenomenex, Inc., Torrance, CA)(150 x 30 mm, 5 muiotaeta) eluting with 0.10% trifluroacetic acid in acetonitrile-water, gradient of 10% to 90% over 10 min) to give N-(l-benzofuran-2-yl(2-fluoro-6- methylphenyl)methyl)-3,4-dihydro-2H-l,5-benzodioxepine-7-sulfonamide (0.013 g) as a yellow film (racemic mixture).1H NMR (300 MHz, methanol-d4) delta 7.48 (m, 1 H), 7.36 – 7.30 (m, 2 H), 7.25 – 7.14 (m, 5 H), 6.97 (d, J= 6.0 Hz 1 H), 6.86 (d, J= 9.0 Hz, 1 H), 6.80 (m, 1 H), 6.51 (s, 1 H), 6.11 (s, 1 H), 4.20 – 4.15 (m, 2 H), 4.13 – 4.08 (m, 2 H), 2.41 (s, 3 H), 2.20 – 2.12 (m, 2 H). m/z (ESI, +ve ion) 490.0 (M+Na)+. GK-GKRP EC50 (LCMS/MS) = 0.79 muMu. GK-GKRP IC50 (Binding) = 1.0 muMu.

Statistics shows that 2-Bromo-1-fluoro-3-methylbenzene is playing an increasingly important role. we look forward to future research findings about 59907-13-0.

Reference:
Patent; AMGEN INC.; BARTBERGER, Michael, D.; CROGHAN, Michael, D.; FOTSCH, Christopher, H.; NORMAN, Mark, H.; PENNINGTON, Lewis, D.; REICHELT, Andreas; ST. JEAN, David, J., Jr.; TEGLEY, Christopher, M.; WO2012/138776; (2012); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 6320-40-7, These common heterocyclic compound, 6320-40-7, name is 1,3,5-Tribromo-2-methylbenzene, 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.

Synthesizing of Intermediates A and B 3.3g (10 mmol) of 2,4,6-tribromotoluene was dissolved in 30 mL of diethylether. The resulting solution was cooled to -78 C and 4.4mL (11 mmol) of normalbutylithium (2.5M in Hexane) was slowly added thereto. The resulting solution was stirred at -78C for one hour and 1.48g (11 mmol) of cooper chloride (II) was added thereto at -78C. The reactant product was stirred for 5 hours and cleaned using distilled water and ethylacetate at room temperature. The cleaned ethylacetate layer was dried over MgSO4 and dried under a reduced pressure, thereby producing a crude-product. The pre-product was refined through a column chromatography and the refined result was recrylstallized in dichloromethane and hexane, thereby producing white solid intermediates A and B. Amounts of A and B were 622 mg (yield 25%) and 746 mg (yield: 30%), respectively. Intermediate A : 1H NMR (CDCl3, 400MHz) delta (ppm) 7.74 (d, 4H), 7.18 (d, 4H), 2.06 (s, 6H); 13C NMR (CDCl3, 100MHz) delta (ppm) 142.8, 134.9, 134.5, 131.1, 126.4, 119.4, 19.9 Intermediate B : 1H NMR (CDCl3, 400MHz) delta (ppm) 7.60 (s, 4H), 2.61 (s, 6H); 13C NMR (CDCl3, 100MHz) delta (ppm) 138.3, 137.2, 129,9, 125.8, 23.5

The synthetic route of 6320-40-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Samsung SDI Co., Ltd.; EP1752442; (2007); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 348-57-2, name is 1-Bromo-2,4-difluorobenzene, 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. Recommanded Product: 1-Bromo-2,4-difluorobenzene

2,4-difluorobromobenzene (3 g, 15.5 mmol) and 260 mg of iron filings were placed in a two-neck flask, and 15 ml of dichloromethane was then added thereto. The two-neck flask was cooled in an ice bath, and a solution including bromine (1 ml, 18.7 mmol) and 15 ml of dichloromethane was added dropwise to the two-neck flask using an isobaric funnel. Next, the contents in the two-neck flask were heated under reflux for 3 hours. During heating, brown gas was produced. Then, the temperature was reduced to 20 C., and 50 ml of a sodium metabisulfite (Na2S2O5) aqueous solution (10%) was mixed with the contents in the two-neck flask by stirring for 1 hour for terminating the reaction therein. Thereafter, the contents in the two-neck flask were washed several times with deionized water to collect an organic layer, the organic layer was dehydrated using sodium sulfate (Na2SO4), and the solvent in the organic layer was removed, followed by column chromatography (SiO2, n-hexane), thereby obtaining white crystals (3.5 g, 83% yield). (0067) The spectrum analysis for the white crystals is: 1H NMR (400 MHz, CDCl3): delta 7.74 (t, J=7.6 Hz, 1H), 6.96 (t, J=8.0 Hz, 1H); 19F NMR (376 MHz, CDCl3, 298 K): delta -103.8 (dd, J=7.5 Hz, J=7.5 Hz). The white crystals were confirmed to be Compound L3-1 having a chemical structure represented by

The synthetic route of 1-Bromo-2,4-difluorobenzene has been constantly updated, and we look forward to future research findings.

Reference:
Patent; NATIONAL TSING HUA UNIVERSITY; Chi, Yun; Tong, Bi-Hai; Duan, Tai-Nan; Ku, Hsiao-Yun; Chen, I-Jen; US9219237; (2015); B1;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 22385-77-9,Some common heterocyclic compound, 22385-77-9, name is 1-Bromo-3,5-di-tert-butylbenzene, molecular formula is C14H21Br, 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.

2,6-Bis(aniline)pyridine (500 mg, 1.914 mmol), 3,5-di-t-butyl-bromobenzene (1.26 g, 4.688 mmol), Pd2(dba)3 (87.6 mg, 95.7 mumol), BINAP (128.7 mg, 229.5 mumol) and sodium t-butoxide (552 mg, 5.744 mmol) were dissolved in 15 mL of toluene. The mixture was stirred for 48 h at 90 0C before cooling it to room temperature and quenching the reaction with 20 mL of water. After separation with dichloromethane, the volatiles were removed in vacuo from the organic extract. The obtained orange oil was passed through a silica gel column by a 20:1 mixture of dichloromethane and ethyl acetate and then was triturated from cold methanol and collected by filtration. 854 mg of pale-yellow solid 6a were obtained after a single wash (70 percent yield). 1H NMR (CDCl3) delta: 1.22 (s, 36eta, C(CH3)3), 6.93 (td, 2eta), 6.99 (t, 2H tBu-Ph-H), 7.05 (d, 4eta, tBu-Ph-H), 7.30 (td, 2eta), 7.54 (dd, 2H), 7.66 (d, 4H, Ph-H, Py-H), 7.90 (t, 1eta, Py-H), 9.8 (s, 2eta,NH). 1H-NMR (C6D6) delta: 1.22 (s, 36H, C(CH3)3), 6.86 (td, 2eta, Ph-H), 7.14 (t, 2eta), 7.1-7.2 (d+t, 3H, Py-H), 7.24 (td, 2eta, Ph-H), 7.32 (d, 4eta), 7.52 (dd, 2H, Ph-H), 7.85 (dd, 2eta, Ph-H), 10.14 (s, 2eta,NH). 13C NMR (CDCl3) delta: 31.6 (CH3), 35.0 (C(CH3)3), 114.6, 115.8, 116.1, 118.9, 120.5, 124.7, 130.0, 130.5, 138.5, 141.5, 143.2, 151.9, 157.3.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1-Bromo-3,5-di-tert-butylbenzene, its application will become more common.

Reference:
Patent; CALIFORNIA INSTITUTE OF TECHNOLOGY; AGAPIE, Theodor; GOLISZ, Suzanne; TOFAN, Daniel; BERCAW, John, E.; WO2008/36882; (2008); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

61613-22-7, name is 2-Bromo-N-phenylaniline, 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. Formula: C12H10BrN

After dissolving 10 g of 2-bromo-N-phenylphenylamine in 100 ml of tetrahydrofuran, the reaction temperature was lowered to -78 C,Slowly add 20 ml of 2.5 M butyllithium and stir for 1 h. 11 g of benzophenone was dissolved in 100 ml of tetrahydrofuran and slowlyAfter dropping, the temperature was increased to room temperature and stirred for 12 h. After the reaction has ended, distilled water and methylene chloride will be usedRow extraction and drying by anhydrous magnesium sulfate followed by filtration under reduced pressure gave the solid which was dissolved in 100 ml of acetic acid, 7 ml of sulfuric acid was added dropwise and the mixture was reflux-stirred. After the reaction was completed, the mixture was extracted with distilled water and methylene chlorideThe resulting solid was purified by column chromatography to give Intermediate B-1 (7.1 g, yield 53%).

The synthetic route of 61613-22-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Changchun Hai Purunsi Technology Co., Ltd.; Liu Xiqing; Cai Hui; (24 pag.)CN107400085; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Application of 176317-02-5, A common heterocyclic compound, 176317-02-5, name is 1-Bromo-2,3,4-trifluorobenzene, molecular formula is C6H2BrF3, 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.

Step 1: 5-bromo-2,3,4-trifluorobenzoic acid To a solution of 1-bromo-2,3,4-trifluorobenzene (13.64 g, 64.6 mmol) in THF (120 mL) was added lithium diisopropylamide (2.0 M in THF, 33.9 mL, 67.8 mmol) at -78 C. under nitrogen atmosphere. After stirring for 1 h at -78 C., the mixture was transferred to a bottle with dry ice. The mixture was stirred overnight at room temperature. The reaction was quenched with 10% aqueous HCl (300 mL) and extracted with ethyl acetate (200 mL*3). The combined organic extracts were washed with 5% sodium hydroxide (300 mL). The aqueous layer was acidized to pH 1 and extracted with ethyl acetate (200 mL*3). The combined organic extract was dried over Na2SO4, filtered and concentrated under reduced pressure to afford the desired product (white solid, 13.51 g, 82% yield). 1H NMR (400 MHz, CDCl3): delta 13.94 (s, 1H), 7.95 (m, 1H).

The basis of chemical reaction formula synthesis, the synthesis route is composed of some specific reactions and combined according to certain logical thinking. We look forward to the emergence of more reaction modes in the future.

Reference:
Patent; TIANJIN BINJIANG PHARMA, INC.; Tian, Hongqi; Ji, Conghui; Liu, Chunlei; Kong, Li; Cheng, Ying; Huang, Gongchao; US2014/371278; (2014); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Adding a certain compound to certain chemical reactions, such as: 69038-76-2, name is 4-Bromo-N1-methylbenzene-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 69038-76-2, Computed Properties of C7H9BrN2

After methyl dichloro(methoxy)acetate (2.5 ml) was added to a solution of 4-bromo-N1-methylbenzene-1,2-diamine (1.0 g), N,N-diisopropylethylamine (7.1 ml) in 1,2-dichloroethane (30 ml), the reaction mixture was stirred at room temperature for 1 hour, and then stirred at 60 C. for 3 days. After the reaction mixture was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added thereto, and extraction was carried out using chloroform. After the organic layer was dried over anhydrous sodium sulfate, the desiccant was removed, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate), thereby obtaining methyl 5-bromo-1-methyl-1H-benzimidazole-2-carboxylate (820 mg) as a solid.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 4-Bromo-N1-methylbenzene-1,2-diamine, and friends who are interested can also refer to it.

Reference:
Patent; ASTELLAS PHARMA INC.; Ohnuki, Kei; Azami, Hidenori; Sawada, Yuki; Shin, Takashi; Kuramoto, Kazuyuki; Kikuchi, Shigetoshi; Saito, Tomoyuki; Hamaguchi, Hisao; Nagashima, Takeyuki; US2015/266869; (2015); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 50548-45-3, name is 1-Bromodibenzo[b,d]furan belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. SDS of cas: 50548-45-3

20 g (80 mmol) of dibenzofuran-1-boronic acid, 2.06 g(40.1 mmol) of iodine, 3.13 g (17.8 mmol) of periodic acid, 80 ml of aceticacid, 5 ml of sulfuric acid, 5 ml water and 2 ml chloroform were stirred at 65C for 3 h. After cooling, water was added to the mixture, and the precipitatedsolids were filtered off with suction, and washed three times with water. Thenthe product was recrystallized from dichloromethane / heptane. The yield is25.6 g (68 mmol), equivalent to 85% of theory.

The synthetic route of 50548-45-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Merck Patent GMBH; Faram, Amir Hossain; Yatsi, Anya; Evemilley, Thomas; Grossman, Tobias; Krevor, Jonas Valentine; Tobelmann, Laruese; (100 pag.)KR2016/28524; (2016); A;,
Bromide – Wikipedia,
bromide – Wiktionary