Month: March 2021

These common heterocyclic compound, 156682-52-9, name is 1,4-Dibromo-2,3-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. Application In Synthesis of 1,4-Dibromo-2,3-difluorobenzene

To a fuming nitric acid (15 mL, 353.1 mmol) was added trifluoromethanesulfonic acid (40 mL, 441.4 mmol) dropwise at 0 C under argon atmosphere. A solution of compound 10 (24 g, 88.3 mmol) was added dropwise to the reaction mixture. After 24 h at 50 C, the mixture was quenched with 1 N NaOH aqueous solution. The precipitated material was recovered by filtration and then recrystallizied from ethanol to give 18 g (56%) of compound 11 as a yellow solid. 13C NMR (75 MHz, CDCl3): delta (ppm) 149.9 (dd, 1JC-F = 266.5 Hz and 2JC-F 17.3 Hz), 141.4 (br), 105.7 (dd, 2JC-F = 13.9 Hz and 3JC-F = 11.6). HRMS (m/z, EI+) calcd for C6Br2F2N2O4 359.8198, found 359.8195.

The synthetic route of 1,4-Dibromo-2,3-difluorobenzene has been constantly updated, and we look forward to future research findings.

Reference:
Article; Jeong, Ina; Chae, Sangmin; Yi, Ahra; Kim, Juae; Chun, Ho Hwan; Cho, Jung Hyeong; Kim, Hyo Jung; Suh, Hongsuk; Polymer; vol. 109; (2017); p. 115 – 125;,
Bromide – Wikipedia,
bromide – Wiktionary

Application of 105679-22-9, 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. 105679-22-9, name is 7-Bromo-3,4-dihydro-2H-benzo[b][1,4]oxazine, This compound has unique chemical properties. The synthetic route is as follows.

Step B: ethyl 9-bromo-7-hydroxy-5-oxo-3,5-dihydro-2H-[l,4]oxazino[2,3,4-ij]quinoline-6- carboxylate A mixture of 7-bromo-3,4-dihydro-2H-benzo[b][l,4]oxazine (760 mg, 3.55 mmol) and triethyl methanetricarboxylate (3298 mg, 14.20 mmol) was heated to 250 C and stirred for 0.5 h. The resulting mixture was cooled to room temperature. The product was recrystallised from petroleum ether (50 mL) to give ethyl 9-bromo-7-hydroxy-5-oxo-3,5-dihydro-2H- [l,4]oxazino[2,3,4-ij]quinoline-6-carboxylate as a solid. XH NMR (CDC13, 400 MHz): delta 14.25 (s, 1H), 7.88 (d, J= 1.6 Hz, 1H), 7.33 (d, J= 1.6 Hz, 1H), 4.52 (q, J= 6.8 Hz, 14.0 Hz, 2H), 4.36 (t, J= 5.2 Hz, 2H), 4.21 (t, J= 5.2 Hz, 2H), 1.49 (t, J= 6.8 Hz, 3H).

The chemical industry reduces the impact on the environment during synthesis 7-Bromo-3,4-dihydro-2H-benzo[b][1,4]oxazine. I believe this compound will play a more active role in future production and life.

Reference:
Patent; MERCK SHARP & DOHME CORP.; MSD R&D (CHINA) CO., LTD.; CAI, Jiaqiang; CRESPO, Alejandro; DU, Xiaoxing; DUBOIS, Byron Gabriel; GUIADEEN, Deodialsingh; KOTHANDARAMAN, Shankaran; LIU, Ping; LIU, Rongqiang; QUAN, Weiguo; SINZ, Christopher; WANG, Liping; (285 pag.)WO2016/49099; (2016); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 399-94-0,Some common heterocyclic compound, 399-94-0, name is 1-Bromo-2,5-difluorobenzene, molecular formula is C6H3BrF2, 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 B: tert-Butyl [1-(2,5-difluorophenyl)-1-oxopent-4-yn-2-yl]carbamate An inerted vessel was charged dichloromethane (866 kg) and cooled to -20 to -10 C. Then iso-propylmagnesium chloride solution in THF (2M, 326.1 kg, 669 mol) was slowly added followed by 1-bromo-2,5-difluorobenzene (120.1 kg, 622 mol). After 2 h at this temperature, an additional charge of iso-propylmagnesium chloride in THF solution was slowly added (2M, 58.65 kg, 121 mol) and the reaction aged 1 h. Then, a drop-wise addition of a dichloromethane solution of tert-butyl (1-[methoxy(methyl)amino]-1-oxopent-4-yn-2-yl)carbamate (70.8 kg, 276 mol in 292 kg dichloromethane) was conducted over 2 h at -20 to -20 C. The mixture was then warmed to room temperature and stirred for 10 h. The reaction was then slowly reverse quenched into aqueous ammonium chloride (175.6 kg in 1550 kg of water) at 5-10 C. The solution pH was then adjusted to ?7 by adding 68 kg of con. HCl. The layers were then separated and the aqueous extracted with dichloromethane (414 kg). The combined organics were then dried with Na2SO4, filtered, treated with activated carbon (10 kg), filtered, and concentrated to 71-141 L. A constant volume (71-141 L) vacuum distillation solvent switch to n-heptane was then performed to crystallize the product. The slurry was then cooled to 0 C. and stirred 2 h. The slurry was filtered and the cake washed with n-heptane, 2-propanol, and then water. The solids were dried under vacuum at 40-50 C. overnight to give tert-butyl [1-(2,5-difluorophenyl)-1-oxopent-4-yn-2-yl]carbamate.

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-2,5-difluorobenzene, its application will become more common.

Reference:
Patent; Merck Sharp & Dohme Corp; Merck Sharp & Dohme Ltd.; Arroyo, Itzia Z.; Krueger, Davida; Chen, Ping; Moment, Aaron J.; Biftu, Tesfaye; Sheen, Faye; Zhang, Yanfeng; US9181262; (2015); B2;,
Bromide – Wikipedia,
bromide – Wiktionary

Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps, and cheap raw materials. 13633-25-5, name is 1-Bromo-4-phenylbutane, A new synthetic method of this compound is introduced below., name: 1-Bromo-4-phenylbutane

Under nitrogen protection, p-methyliodobenzene (0.1 mmol), sodium metabisulfite (0.2 mmol, 2.0 equiv.), Tin powder (0.3 mmol, 3.0 equiv.), 1,1′-bis (diphenylphosphino) Ferrocene palladium dichloride (0.01 mmol, 10 mol%), 1,1′-bis (diphenylphosphine) ferrocene (0.02 mmol, 20 mol%), dipotassium hydrogen phosphate trihydrate (0.2 mmol, 2.0 equiv .), Tetrabutylammonium bromide (0.15 mmol, 1.5 equiv.) Was added to the reaction tube containing the magneton, and after nitrogen evacuation three times, bromophenylbutane (0.3 mmol, 3.0 equiv.) Was added, and DMSO ( 1.0mL), the reaction system was heated to 100 C for 10 hours, and the reaction was completed by spot detection. After the aryl iodide was completely converted, the reaction system was cooled to room temperature, diluted with water and added with ethyl acetate (10mL * 3) for extraction. Anhydrous sulfuric acid Sodium was dried, filtered, concentrated, and separated by column chromatography to obtain the purified target product 3ad (72%).

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; East China Normal University; Jiang Xuefeng; Meng Yingying; Wang Ming; (40 pag.)CN110563619; (2019); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 4549-33-1, These common heterocyclic compound, 4549-33-1, name is 1,9-Dibromononane, 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.

General procedure: A mixture of 5,6-dimethoxy-1-oxo-indan-2-carboxylic acid ethyl ester 14 (235 mg, 0.88 mmol) and NaH (79.5 mg, 2.65 mmol, 80% dispersion in mineral oil) in DMF (8 mL) was stirred at room temperature for 30 min, after which 1-chloro-3-iodo propane (0.185 mL, 1.76 mmol) was added. The reaction mixture was stirred at room temperature for 20 h and quenched by adding water (15 mL) and aqueous HCl (1 mL, 1.0 N). The mixture was extracted with dichloromethane (3 * 20 mL), and the combined organic layers were washed with brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (silica gel, EtOAc/PE, 1/4) to generate the title compound (200 mg, 66%) as pale yellow oil.

The synthetic route of 4549-33-1 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Hu, Yueqing; Zhang, Jun; Chandrashankra, Oormila; Ip, Fanny C.F.; Ip, Nancy Y.; Bioorganic and Medicinal Chemistry; vol. 21; 3; (2013); p. 676 – 683;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 17247-58-4, 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. 17247-58-4 name is (Bromomethyl)cyclobutane, 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.

500 mg (2.00 mmol) of the compound from Ex. 31A and 690 mg (5.00 mmol) of potassium carbonate were stirred in 10 ml of anhydrous DMF at RT for 15 min, before 449 mul (4.00 mmol) of (bromomethyl)cyclobutane were added. Then the reaction mixture was stirred at 50 C. for about 16 h. After cooling to RT, water was added and the mixture was extracted with ethyl acetate. The organic extract was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated. The product was isolated by means of MPLC (Biotage Isolera One, SNAP KP-Sil cartridge, 50 g of silica gel, eluent: cyclohexane/ethyl acetate 2:1). After concentration of the product fractions and drying under high vacuum, 486 mg (76% of theory) of the title compound were obtained. 1H-NMR (400 MHz, DMSO-d6, delta/ppm): 10.07 (s, 1H), 3.96 (d, 2H), 2.82-2.69 (m, 1H), 2.76 (s, 3H), 2.66-2.58 (m, 1H), 2.04-1.91 (m, 2H), 1.89-1.74 (m, 4H), 1.07-0.96 (m, 2H), 0.73-0.64 (m, 2H). LC/MS (Method 1, ESIpos): Rt=1.89 min, m/z=319.11 [M+H]+.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, (Bromomethyl)cyclobutane, and friends who are interested can also refer to it.

Reference:
Patent; Bayer Aktiengesellschaft; Bayer Pharma Aktiengesellschaft; HAERTER, Michael; KOSEMUND, Dirk; CANCHO GRANDE, Yolanda; DELBECK, Martina; KALTHOF, Bernd; LUSTIG, Klemens; SUESSMEIER, Frank; US2020/16159; (2020); 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. 1003-98-1, name is 2-Bromo-4-fluoroaniline belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. Recommanded Product: 2-Bromo-4-fluoroaniline

Example 100:; To a DMF solution (7ml_) of 4-fluoro-2-bromoaniline (258mg, 1.36mmol) was added the alkyne 92a (400mg, 1.36mmol), Pd(PPh3)2CI2 (38mg, 0.054mmol), CuI (20.6mg, O.H mmol) and i- Pr2NH (2 mL). The mixture was degassed in vacuo, flushed with nitrogen and heated at 90C for 1 h. The resulted solution was diluted with EtOAc (3OmL), washed with brine (2x25mL), dried (MgSO4) and concentrated in vacuo. The residue was purified with silica gel column chromatography (15% EtOAc in hexanes) giving the title compound (320mg, 58% yield) as a solid. ). LCMS (APCI positive): 405 (M+H+).

The synthetic route of 1003-98-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; PFIZER, INC.; WO2006/40646; (2006); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 149910-98-5, name is 7-Bromoisochroman, 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: 149910-98-5

General procedure: To a solution of the substituted isochroman derivatives (0.5 mmol) in MeCN (1 mL), CuBr2(0.6 mmol, 134 mg) was added under nitrogen atomosphere. The solution wasrefluxed for about 1h and then cooled to room temperature. The reaction mixturewas added water, extracted with EtOAc (2 ¡Á 10 ml). The combined organicextracts were washed with brine, dried (Na2SO4), filteredand concentrated and then purified by silicagel chromatography.

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

Reference:
Article; Zhou, Mei-Yan; Kong, Shan-Shan; Zhang, Ling-Qiong; Zhao, Ming; Duan, Jin-Ao; Ou-Yang, Zhen; Wang, Min; Tetrahedron Letters; vol. 54; 30; (2013); p. 3962 – 3964;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 103-64-0,Some common heterocyclic compound, 103-64-0, name is (2-Bromovinyl)benzene, molecular formula is C8H7Br, 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.

To a solution of N, N-dimethylformamide (DMF) in a volume ratio of 4: 1 with polyethylene glycol 200(PEG-200)) was added 100 mmol of the compound of the above formula (I), 70 mmol of the compound of the above formula (II), 10 mmol of catalyst bis (triphenylphosphine) cyclopentadienyl ruthenium chloride,(TDI) 2), 12 mmol of organic ligand L1 and 70 mmol of base, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), Then stirred to a temperature of 90 C, and the reaction was stirred at that temperature for 9 hours;After completion of the reaction, the reaction system is naturally cooled to room temperature and the pH is adjusted to neutral, filtered and the filtrate is saturatedSalt water washing, and then extracted with ethyl acetate 2-3 times,The combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography eluting with a 1: 2 by volume mixture of chloroform and petroleum ether to give the compound of formula (III) Was 93.9%.

The synthetic route of 103-64-0 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Huang, Cheng; No proclaimed inventor; (12 pag.)CN106278839; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 626-40-4,Some common heterocyclic compound, 626-40-4, name is 3,5-Dibromoaniline, molecular formula is C6H5Br2N, 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.

General procedure: All the final reactions (11a-n) were performed by 200 mg scale. To a stirred solution of acid compound 9 (1.0 equiv) and substituted aromatic amines (10a-n) (1.0 equiv) in dichloromethane was added EDCI (1.0 equiv), HOBt (1.0 equiv) and DIPEA (1.2 equiv) at room temperature. The reaction mixture was stirred for 12 h. After completion of the reaction as monitored by TLC, the reaction mixture was diluted with dichloromethane, washed with saturated solution of NaHCO3, dried over anhydrous Na2SO4, filtered and concentrated. The crude products were purified by column chromatography eluted with ethyl acetate/hexane to afford the pure compounds (11a-n).

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

Reference:
Article; Venkat Swamy, Puli; Kiran Kumar, Vukoti; Radhakrishnam Raju, Ruddarraju; Venkata Reddy, Regalla; Chatterjee, Anindita; Kiran, Gangarapu; Sridhar, Gattu; Synthetic Communications; vol. 50; 1; (2020); p. 71 – 84;,
Bromide – Wikipedia,
bromide – Wiktionary