Month: November 2020

These common heterocyclic compound, 327-51-5, name is 1,4-Dibromo-2,5-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. 327-51-5

To a -78 C solution of 1 ,4-dibromo-2,5-difluorobenzene (2.72 g, 9.99 mmol) in dry Et20 (30 mL) under an inert atmosphere was added 2.5 M n-butyl lithium solution in hexanes (4 mL, 9.99 mmol) dropwise and the mixture left stirring for 2 h. Crushed CO2 pellets were added slowly and the mixture was allowed to warm to ambient temperature and left stirring for 1 h. After quenching with 1 M aq. HCI (10 mL) the mixture was basified with 1 M aq. NaOH (70 mL) and then washed with Et20 (2 x 50 mL). The aqueous layer was acidified with 1 M aq. HCI (80 mL) and extracted with Et20 (3 x 100 mL). The organic layer was washed with brine (50 mL), dried over Na2S04, filtered and solvent was removed in vacuo to give 4-bromo-2,5- difluoro benzoic acid (2.3 g, 97 %) as an off-white solid, which was used without further purification. SUBSTITUTE SHEET RULE 26 1 H NMR (Method B) (CDC ): delta ppm 9.50 (br s, 1 H), 7.78 (dd, J = 8.2, 6.1 Hz, 1 H), 7.46 (dd, J = 9.3, 5.4 Hz, 1 H); LC-MS (Method C) 234.9/236.9 [M-H]+; RT 3.43 min

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 327-51-5.

Reference:
Patent; REDX PHARMA PLC; HUXLEY, Anthony; KIRK, Ralph; RATCLIFFE, Andrew; LYTH, David; (112 pag.)WO2017/46605; (2017); 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

Preparation 502-(3,5-Di-tert-butylphenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane Bubble nitrogen through DMF (150 mL) for about 15 min prior to adding the reagents. Then dissolve l-bromo-3,5-di-tert-butylbenzene (20.93 g, 77.74 mmol), bis(pinacolato)diboron (22.70 g, 89.40 mmol), and (Iota, – bis(diphenylphosphino)ferrocene)palladium(II) chloride (3.17 g, 3.89 mmol) in the DMF. Stir for 10 min. Add potassium acetate (22.89 g, 233.23 mmol) and bubble argon through the solution for 7 min. Heat the reaction to 85 ¡ãC with stirring for 24 h. Dilute the reaction with water (1.5 L). Collect the resulting brown precipitate by vacuum filtration and washing with water. Dissolve the residue in dichloromethane. Dry this solution over sodium sulfate, filter; collect the filtrate; and concentrate under reducedpressure. Triturate the resulting solids with hot hexanes (400 mL) and filter, washing with hexanes. Concentrate the filtrate to a volume of approximately 300 mL. Place the solution in a freezer overnight. Collect the solid by vacuum filtration and rinsing with cold hexanes. Concentrate the filtrate under reduced pressure to a volume of 150 mL. Cool this mixture in the freezer for about 1.5 h. Collect the resulting solids by vacuum filtration and rinse with cold hexanes. Combine the 2 crops and dry under high vacuum to afford the title compound (21.85 g, 89percent) as a light tan crystalline solid. XH NMR (400 MHz, CDC13) delta 1.33 (s, 12H), 1.33 (s, 18H), 7.53 (t, J = 2.0 Hz, 1H), 7.65 (d, J = 2.0 Hz, 2H).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-3,5-di-tert-butylbenzene, and friends who are interested can also refer to it.

Reference:
Patent; ELI LILLY AND COMPANY; BLEISCH, Thomas, John; COATES, David, Andrew; HUGHES, Norman, Earle; JONES, Scott, Alan; NORMAN, Bryan, Hurst; WO2013/66640; (2013); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 1435-51-4, name is 1,3-Dibromo-5-fluorobenzene, 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. 1435-51-4

9H-pyrido[2,3b]indole (5.04 g, 30.00 mmol, 1.0 eq) was sequentially added to a dry reaction tube with a magnetic rotor.CuI (571.4 mg, 3.00 mmol, 0.01 eq),L-Proline (690.0mg,6.00mmol, 0.02eq) andK2CO3 (8.29 g, 60.00 mmol, 2.0 eq).Pumping nitrogen three times,Then added 1,3-dibromo-5-fluorobenzene (9.14 g, 36.0 mmol, 1.2 eq) andSolvent dimethyl sulfoxide (30 mL).The reaction mixture was placed in an oil bath at 120 C for 1.5 days.Cool to room temperature, add 100 mL of ethyl acetate and dilute with Celite.And fully washed with ethyl acetate, added50mL of water, liquid separation, ethyl acetate extraction of the aqueous phase three times, the organic phase was combined, the organic phase was dried over anhydrous sodium sulfate, filtered, the solvent was evaporated under reduced pressure, the crude product was purified by silica gel column chromatography, eluent (petroleum ether) /methylene chloride = 4:1-2:1),Obtained a white solid 2-Br-F 3.22g,The yield was 31%. The product was used directly in the next step of synthesis.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 1435-51-4.

Reference:
Patent; Zhejiang University of Technology; Ruisheng Optoelectric Science And Technology (Changzhou) Co., Ltd.; Li Guijie; She Yuanbin; Zhao Xiangdong; Chen Shaohai; (33 pag.)CN108948095; (2018); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Adding some certain compound to certain chemical reactions, such as: 327-52-6, name is 1-Bromo-2,4,5-trifluorobenzene, 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 327-52-6. 327-52-6

To magnesium spalls in a reaction flask, under an atmosphere of nitrogen, was added 50 ml tetrahydrofuran and 0.02 g iodine as an initiator. A solution of 9 g 1-bromo-2,4,5-trifluorobenzene in 150 ml tetrahydrofuran was added dropwise into the reaction system. The reaction was stirred at 25 C. for 3 h to obtain a solution of 0.21 mol/L (2,4,5-trifluorophenyl)-magnesium bromide.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 1-Bromo-2,4,5-trifluorobenzene.

Reference:
Patent; ZHEJIANG JIUZHOU PHARMACEAUTICAL CO., LTD.; Gao, Hongjun; Li, Min; US2013/12735; (2013); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

49764-63-8,Some common heterocyclic compound, 49764-63-8, name is 4,5-Dibromobenzene-1,2-diamine, molecular formula is C6H6Br2N2, 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 solution of intermediate 6 (1.0 equiv.) and substituted o-phenylenediamine (1.0 equiv.) in 15 mL acetonitrile was stirred at roomtemperature overnight. TLC was used to monitor the progress of the reaction. When the reaction finished, the mixture was addedBOP (1.5 equiv.) and DBU (2.0 equiv.) and was stirred at room temperature. TLC was used to monitor the progressof the reaction. The solutionwas treated with water and ethyl acetate. The organic phases were combined anddried over and evaporated to dryness under reduced pressure. Purification bychromatography using petroleum ether/ethyl acetate 2:1 yielded 7a.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 49764-63-8, its application will become more common.

Reference:
Article; Bu, Huagang; Jia, Lejiao; Li, Jun; Li, Zhenyu; Li, Zhiying; Shen, Chengwu; Tang, Hui; Wu, Xingkang; Zhang, Rui; Bioorganic and medicinal chemistry letters; (2020);,
Bromide – Wikipedia,
bromide – Wiktionary

3814-30-0, Name is (Bromomethyl)cyclopentane, 3814-30-0, 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.

Weigh 165.7mg (1.02mmol) of bromomethylcyclopentane and dissolve it in DMF, add it dropwise to the reaction flask and stir for 5min, and dropwise add 73mg (1.12mmol) of sodium azide solution ( DMF solution), argon protection, 100 C reflux stirring reaction for 12h, complete reaction was detected by TLC, add pure water, extract with EtOA, wash with water, dry with MgSO4, filter with suction and concentrate the dried product, then dissolve its EtOAc and add dropwise to the reaction flask During stirring for 5 min, 110 mg (1.02 mmol) of p-benzoquinone (EtOAc dissolved) was added dropwise, protected by argon, and the reaction was stirred at 70 C under reflux for 24 h. The reaction was completed by TLC, the reaction was terminated, and the crude product was obtained by concentration and drying. The crude product was separated by Combiflash (RediSep Column: Silica 20g, column retention volume was 78ml), and the elution gradient was EtOAc: PE = 20:80. The fractions were analyzed by TLC, combined and dried to obtain 22.5mg of compound ZY011901 and 22.5mg of compound ZY011903

Statistics shows that (Bromomethyl)cyclopentane is playing an increasingly important role. we look forward to future research findings about 3814-30-0.

Reference:
Patent; Guangzhou University Of Traditional Chinese Medicine (Guangzhou Traditional Chinese Medicine Institute); Liu Jiawei; Yu Qiang; Zheng Yangqing; Zhang Qing; Ma Hongyan; Zeng Xinling; Zhou Qing; Wen Liangxi; Liu Jingli; Li Min; Xia Fan; (49 pag.)CN110872299; (2020); A;,
Bromide – Wikipedia,
bromide – Wiktionary

1435-51-4, 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. 1435-51-4 name is 1,3-Dibromo-5-fluorobenzene, 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.

Sodium methoxide (8.80 ml of a 4.5M solution in methanol, 39.6 mmol) was added dropwise to a stirred solution of 3,5-dibromofluorobenzene (5.00 g, 19.0 mmol) in N,N-dimethylformamide (95 ml) at 0 C. under nitrogen. The reaction was allowed to warm to room temperature, stirred for 1 hour and then concentrated under reduced pressure. The residue was dissolved in ether (500 ml) and the resulting solution was washed with water (3¡Á300 ml) and brine (300 ml), dried over magnesium sulphate, filtered and concentrated under reduced pressure to provide the title compound (5.13 g) as a white solid. 1H-NMR (300 MHz, CDCl3): delta=3.79 (s, 3H), 7.00 (s, 2H), 7.26 (s, 1H). LRMS (thermospray): m/z [MH+] 266. Microanalysis: Found: C, 31.56; H, 2.29. C7H6OBr2 requires C, 31.62; H, 2.27%.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1,3-Dibromo-5-fluorobenzene, and friends who are interested can also refer to it.

Reference:
Patent; Pfizer Inc.; US2005/54707; (2005); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

4549-33-1, 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 4549-33-1 as follows.

4-Picoline (2.0 mL, 21 mmol) was dissolved in THF (40 mL) under an argon atmosphere using a 150 mL Schlenk flask. The Schlenk flask was cooled down to-78C by using a dry ice/methanol cooling bath. A solution of n-butyllithium in hexane (12.0 mL, 18 mmol) was added to the solution by a syringe under an argon atmosphere. After the solution was stirred for 30 min, diethyl amine (2.2 mL, 22 mmol) was added to the solution by a syringe under an argon atmosphere. After the solution was stirred for 30 min, the solution was added to a solution of 1,9-dibromononane (20.0 mL, 99 mmol) in THF (10 mL) by a syringe under an argon atmosphere. The reaction mixture was gradually warmed to room temperature and stirred for 1 h. The solution was poured into 0.5M ammonium chloride (10 0mL) to quench the reaction at 0C. After evaporation of the organic solvent at 0C, the residual solution was dropped into 1M hydrobromic acid (100 mL), and the product was extracted with dichloromethane (4¡Á50 mL). The organic layers were combined, and dried with sodium sulfate (15 g). The organic layer was concentrated under reduced pressure. After the residual solution was dropped into hexane (200 mL), and then a pale yellow precipitate was formed. The pale yellow precipitate containing the product was recovered by centrifugation. The product 1 was obtained as a pale yellow powder (yield 5.12g, 65%). 1H NMR (500MHz, DMSO-d6): delta 8.42 (d, J=5.9Hz, 2H), 7.19 (d, J=5.9Hz, 2H), 3.50 (t, J=6.7Hz, 2H), 2.57 (t, J=7.6Hz, 2H), 1.81-1.72 (m, 2H), 1.61-1.52 (m, 2H), 1.39-1.20 (m, 12H).

According to the analysis of related databases, 1,9-Dibromononane, the application of this compound in the production field has become more and more popular.

Reference:
Article; Hashidzume, Akihito; Kuse, Akihiro; Oshikiri, Tomoya; Adachi, Seiji; Yamaguchi, Hiroyasu; Harada, Akira; Tetrahedron; vol. 73; 33; (2017); p. 4988 – 4993;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 1559-88-2, name is 3-Bromo-1,2,4,5-tetrafluorobenzene, 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. 1559-88-2

General procedure: An oven-dried Schlenk tube equipped with a stir bar was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol, 10 mol%), aryliodine(III) diacetate (0.24 mmol) and Ag2CO3 (82.7 mg, 0.3 mmol). The tube was fitted with a rubber septum, and then it was evacuated and refilled with nitrogen three times. Under nitrogen, polyfluoroarene (0.2 mmol), DMSO(0.1 mL) and DMF (2 mL) were added successively. The rubber septum was replaced with a Teflon screw cap under nitrogen flow. With stirring, the reaction mixtures were heated at 110 C for the indicated amount of time (unless otherwise specified), and then cooled down to roomtemperature. The resultant mixture was filtered through a short plug of silica gel and then concentrated in vacuo. The residue was then purified by flash chromatography on silica gel to provide the corresponding product.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 1559-88-2.

Reference:
Article; Fu, Zhengjiang; Xiong, Qiheng; Zhang, Wenbiao; Li, Zhaojie; Cai, Hu; Tetrahedron Letters; vol. 56; 1; (2015); p. 123 – 126;,
Bromide – Wikipedia,
bromide – Wiktionary

6138-90-5, 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. 6138-90-5, name is Geranyl bromide belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

EXAMPLE 26 (4E)-2-(4Methoxy-benzenesulfonyl)-5,9-dimethyl-2-[4-(2-morpholin-4-yl-ethoxy) -benzyl]-deca-4,8-dienoic acid hydroxyamide To a stirred solution of (4-methoxy-benzenesulfonyl)-acetic acid ethyl ester (5.16 g, 20 mmol), geranyl bromide (4.2g, 20 mmol) and 18-Crown-6 (500 mg) in acetone (250 ml) was added K2CO3 (10 gms, excess) and the mixture refluxed foe 24 hours. At the end, the reaction mixture was filtered and the acetone layer was concentrated. The residue obtained was extracted with chloroform, washed well with water, dried over anhydrous MgSO4, filtered and concentrated. The product obtained was purified by silica-gel column chromatography, eluding with 30% ethy acetate: hexane. The product 2-(4-methoxy-benzenesulfonyl)-5,9-dimethyl-deca-4,8-dienoic acid ethyl ester was isolated as a colourless oil. Yield: 7.0 g, 89%.

The synthetic route of Geranyl bromide has been constantly updated, and we look forward to future research findings.

Reference:
Patent; American Cyanamid Company; US6172057; (2001); B2;,
Bromide – Wikipedia,
bromide – Wiktionary