Author: tianli

These common heterocyclic compound, 28342-75-8, name is 1,5-Dibromo-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. 28342-75-8

General procedure: E1 (3.00 equivalents), E2 (1 .00 equivalents) and E3 (1 .00 equivalents) were dissolved in dry DMF, NaH (6.00 equivalents) was added and the reaction mixture was stirred at 50 ¡ãC over night. Subsequently, NaH (3.00 equivalents) was added to the reaction mixture. The reaction mixture was poured on water and extracted repeatedly with dichloromethane. The combined organic layer was dried over sodium sulfate (Na2S04). The solvents were evaporated under reduced pressure to obtain Z1. Z1 (1 .00 equivalents) was dissolved in tert-butylbenzene and the solution was cooled to -30 ¡ãC. tert-Butyllithium (‘BuLi) (4.00 equivalents) was added dropwise and the reaction mixture was slowly heated up to 0 ¡ãC. After stirring for 30 minutes at 0 ¡ãC, the reaction mixture was cooled again to -30 ¡ãC. (0229) A solution of boron tribromide (BBr3, 2.2 equivalents) was added dropwise, the bath was removed and the reaction mixture was allowed to warm to room temperature (RT). Subsequently, the reaction mixture was heated at reflux at 120 ¡ãC for 5h. Volatiles were removed under reduced pressure to obtain Z3. (0230) A solution of Grignard compound/compounds [R1MgBr (1 .5 equivalents) / R2MgBr (1.5 equivalents)] was added dropwise to Z3 over a period of 30 min. After stirring for 1 h, MeOH was added to the reaction mixture and the solvents were evaporated under reduced pressure. The residue was dissolved in toluene and filtered with a pad of silica gel (toluene was used as eluent). The solvent was removed under reduced pressure. The crude product was dissolved in a minimum amount of toluene and then a small amount of heptane was added. The resulting precipitate was filtered to obtain P1 as a solid 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 28342-75-8.

Reference:
Patent; CYNORA GMBH; SEIFERMANN, Stefan; (41 pag.)WO2019/52940; (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. 38573-88-5 name is 1-Bromo-2,3-difluorobenzene, 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. 38573-88-5

(6S,9R)-6-(2,3-Difluorophenyl)-9-(triisopropylsilyloxy)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one. See Fox, J. M.; Huang, X.; Chieffi, A.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 1360-1370. In an oven-dried 1 L flask was Sodium tert-butoxide (13.19 g, 137 mmol), PALLADIUM(II) ACETATE (0.948 g, 4.22 mmol), and 2-(Dicyclohexylphosphino)-2′-methylbiphenyl (1.539 g, 4.22 mmol) weighed in a nitrogen bag. (R)-9-(triisopropylsilyloxy)-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-5-one (35.21 g, 106 mmol), Toluene (106 mL) (degassed in the original bottle by nitrogen gas), and 1-bromo-2,3-difluorobenzene (14.18 mL, 127 mmol) were added under nitrogen. The flask stirred at 80¡ã C. in a pre-heated oil bath for 20 h. Volatiles were stripped off and the residue was partitioned between EtOAc (400 ml) and water (400 ml). The layers were separated. The aqueous layer was extracted with EtOAc (50 ml). The combined organic layer was washed with brine, dried and concentrated to a dark oil. It was passed through a plug of silica gel (loaded with CH2Cl2 and eluted with EtOAc/hexane up to 30percent EtOAc). The crude product was obtained as a dark red oil (86percent mass recovery),. 1H NMR showed approximately 6/1 ratio of the desired trans isomer to the cis isomer. MS(ESI)[M+H+]=446.21.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-2,3-difluorobenzene, and friends who are interested can also refer to it.

Reference:
Patent; Bristol-Myers Squibb Company; US2009/258866; (2009); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

A common compound: 51554-93-9, name is 1-Bromo-4-octylbenzene, 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. 51554-93-9

To synthesize intermediate compound 16d, n-BuLi (2.5 M in hexane, 146 muIota_, 0.364 mmol) is added dropwise to a solution of 1 -bromo-4-octylbenzene (16a) (94 mg, 0.350 mmol) in THF (0.53 ml_) at -78 C. After stirring for 0.5 h, 16c (40 mg, 0.14 mmol) in THF (0.1 ml_) is added to the mixture, and the solution is stirred for an additional 2 h at-78 C. The reaction is then warmed to -40 C and stirred overnight. The reaction mixture is quenched at -40 C with saturated NH4CI solution and allowed to warm to room temperature. The organic layer is separated and the aqueous layer is extracted three times with CH2CI2. The combined organic layers are washed with brine, dried over MgS04 and filtered. The solvent is removed under reduced pressure and the residue is purified by flash chromatography (hexane: EtOAc, 12: 1 to 8: 1 ) to give compound 16d (21 mg, 32 %) as a slightly yellow oil.

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, 51554-93-9, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; THE REGENTS OF THE UNIVERSITY OF CALIFORNIA; THE UNIVERSITE DE MONTREAL; EDINGER, Aimee; HANESSIAN, Stephen; (172 pag.)WO2017/53990; (2017); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

51436-99-8, 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 51436-99-8 as follows.

Add sodium hydride (60% dispersion in oil, 880 mg, 22 mmol) to a solution OF 4- HYDROXY-L-METHYL-PIPERIDINE (2. 304 g, 20 mmol) in DMF (12 mL), stir. After 30 min., add 4-BROMO-2-FLUOROTOLUENE (4.159 g, 22 mmol) and heat at 70 C. After 21 hr. , quench the reaction with saturated NAHC03 solution, extract with ether three times, combine the organic layers, wash with saturated NaCl solution, dry over NA2SO4, filter and concentrate to give a residue. Purify by chromatography (silica gel, eluting with 6% 2M NH3- methanol in CH2CI2) provides of the title compound as a slightly yellow oil (3.90 g, 69%). Mass spectrum (ion spray): m/z = 284.0 (M ;’H NMR (CDCI3, ppm): 7.01 (m, 3H), 4.35 (m, 1H), 2.66 (m, 2H), 2.36 (m, 2H), 2.34 (s, 3H), 2.19 (s, 3H), 2.03 (m, 2H), 1.85 (m, 2H).

According to the analysis of related databases, 4-Bromo-2-fluorotoluene, the application of this compound in the production field has become more and more popular.

Reference:
Patent; ELI LILLY AND COMPANY; WO2004/94380; (2004); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 558-13-4, name is Carbontetrabromide, 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. 558-13-4

To an ice cold solution of the hexanol (ca. 19.8 mmoles) and carbon tetrabromide (21.98 mmoles) in methylene chloride (50 ml) was added triphenylphosphine (22.30 mmoles) in methylene chloride (50 ml) and the resulting solution was stirred for 2.5 hours. The volatiles were evaporated and the residue was taken up in ether (100 ml), cooled in ice, and filtered The filtrate was evaporated and distilled to afford 6-phenylhexyl bromide as an oil.

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 558-13-4.

Reference:
Patent; SmithKline Beckman Corporation; US4730005; (1988); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Some common heterocyclic compound, 1435-51-4, name is 1,3-Dibromo-5-fluorobenzene, molecular formula is C6H3Br2F, 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

To mixture of l,3-dibromo-5-fluorobenzene (LXX) (100 g, 393 mmol) and N’,N’-dimethylethane-l,2-diamine (173 g, 1.97 mol, 214 mL) was added t-BuOK (88 g, 787 mmol) in one portion at 25C under N2. The mixture was stirred at 25C for 30 min, then heated to 1 10C and stirred for 1 1.5 h. The mixture was cooled to 25C and concentrated in reduced pressure at 45C. The residue was purified by silica gel chromatography (column height: 250 mm, diameter: 100 mm, 100-200 mesh silica gel, PE/EtOAc = 2: 1, Rf = 0.6) to give N:-(3- bromo-5-fluorophenyl)-N2,N2-dimethylethane-l,2-diamine (LXXI) (30 g, 1 14.9 mmol, 29.2% yield) as a yellow oil. ESIMS found for Ci0Hi4BrFN2 mlz 261.1 (M+H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1435-51-4, its application will become more common.

Reference:
Patent; SAMUMED, LLC; KC, Sunil Kumar; WALLACE, David Mark; CAO, Jianguo; CHIRUTA, Chandramouli; HOOD, John; (251 pag.)WO2017/24003; (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. 73918-56-6 name is 2-(4-Bromophenyl)ethanamine, 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. 73918-56-6

General procedure: To a solution of neocrotocembraneic acid (150 mg, 0.50 mmol) in dry CH2Cl2 (10 mL) were added HOBt (81 mg, 0.60 mmol) and EDCI (115 mg, 0.60 mmol). The mixture was stirred at room temperature for 2 h, and then the corresponding amines (0.6 mmol 1.2 equiv.) were added. Upon completion, the reaction mixture was washed successively with 1M hydrochloric acid, saturated NaHCO3 and brine, then dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography to give the amide derivatives 8a-8r.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 2-(4-Bromophenyl)ethanamine, and friends who are interested can also refer to it.

Reference:
Article; Shang, Hai; Li, Ling-Yu; Cheng, Wei-Hua; Luo, Jun; Zhang, Hong-Wu; Zou, Zhong-Mei; Molecules; vol. 21; 11; (2016);,
Bromide – Wikipedia,
bromide – Wiktionary

1435-51-4, 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. 1435-51-4, name is 1,3-Dibromo-5-fluorobenzene, This compound has unique chemical properties. The synthetic route is as follows.

General procedure: To 2,6-dimethoxyphenylboronic acid (4.50 mmol, 819 mg) in a mixture of toluene (45.0 mL), 2 M aqueous Na2CO3 (18.0 mL) and EtOH (9 mL) were successively added under Argon 1-fluoro-3-iodo-benzene (3.00 mmol, 666 mg) and Pd(PPh3)4 (0.15 mmol, 173 mg). This well-stirred mixture was heated at reflux for 18 h and then diluted at 25 C with water (100 mL) and toluene (50 mL). The aqueous layer was separated and washed with CH2Cl2 (2 ¡Á 100 mL). All the organics layers were combined, dried over Na2SO4 and concentrated under reduced pressure. Purification of the residue by column chromatography (cyclohexane/CH2Cl2 75:25) followed by crystallization from MeOH afforded biaryl 4a as a colorless solid (380 mg, 55%).

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Article; Diemer, Vincent; Garcia, Juan Sanz; Leroux, Frederic R.; Colobert, Francoise; Journal of Fluorine Chemistry; vol. 134; (2012); p. 146 – 155;,
Bromide – Wikipedia,
bromide – Wiktionary

69272-50-0, name is 3,6-Dibromobenzene-1,2-diamine, 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. 69272-50-0

Dissolve 3,6-dibromobenzene-1,2-diamine (10g, 37mmol) and 1,2-diphenyl-1,2-ethanedione (7.9g, 37mmol) in ethanol (250ml, 0.15M) in a two-neck round bottom flask And refluxed under nitrogen at 100 C. for one day.The temperature was lowered to room temperature and filtered to obtain Compound 2-A (light yellow solid). (Yield 16g, Yield 96%)

Statistics shows that 69272-50-0 is playing an increasingly important role. we look forward to future research findings about 3,6-Dibromobenzene-1,2-diamine.

Reference:
Patent; LG Chem, Ltd.; Lee Ji-yeong; Kim Sang-a; Ryu Seung-jun; Kim Ji-hun; (26 pag.)KR2019/86210; (2019); A;,
Bromide – Wikipedia,
bromide – Wiktionary

3638-73-1, These common heterocyclic compound, 3638-73-1, name is 2,5-Dibromoaniline, 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.

2,5- dibromo aniline (compound 1, 7.53 g, 30 mmol), Chloral monohydrate (5.95 g, 36 mmol), hydroxy amine – hydrogen chloride (3.13 g, 45 mmol) and sodium sulfate (30.0 g) were added into a mixed solvent of water (100 mL) & ethanol (100 mL). These mixture was heated-refluxed for 12 hours at 80C. Thereafter, ethanol was removed under reduced pressure, concentrated, and when poured into crushed ice, a white solid was precipitated. As it is, allowed to stand for 3 hours at 0C, then the precipitated white solid was recovered by filtration, and dried in air to obtain 8.28 g (86%) of 2,5- dibromo isonitroso acetoanilide (compound 2). Subsequently, this compound 2 was heated for 15 mins at 100C in 86% sulfuric aicd (80 mL), to proceed the cyclization reaction, and the color of the reaction product changes to dark red. Here the resulting product was poured into crushed ice and 4.96 g (63%) of 3,6- dibromo isatin (compound 3) was precipitated as light orange crystals. Then, the produced compound 3 was done hydrolysis under basic conditions by adding hydrogen peroxide and 3.79 g (79%) of 3,6- dibromo Anthranilic Acid (compound 4) was obtained as Dull white crystals. Finally, compound 4 was done diazotization under the existence of nonproton, and by doing this, it is possible to change to 1,4- dibromo- 2,3- diiodo benzene (compound 5). Hexane as eluent, by silica gel column chromatography or by distillation under reduced pressure, compound 5 was obtained as white crystals with yield 35% (2.19 g).

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 3638-73-1.

Reference:
Patent; ADEKA Corporation; Nishihara, Yasushi; Chang, Ning Huei; Iwasaki, Masayuki; (22 pag.)JP6132656; (2017); B2;,
Bromide – Wikipedia,
bromide – Wiktionary