Category: bromides-buliding-blocks

Some common heterocyclic compound, 18599-22-9, name is 4-Bromo-3,3,4,4-tetrafluorobut-1-ene, molecular formula is C4H3BrF4, 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 4-Bromo-3,3,4,4-tetrafluorobut-1-ene

General procedure: In a two-necked round-bottomed flask, equipped with a teflon-coated stirrer bar and reflux condenser, was added ethyl 2-iodobenzoate (3j, 0.14 g 0.50 mmol), Cu2O (0.060 g, 0.42 mmol), and a DMF solution of 2-Zn (0.65 M, 1.54 mL, 1.0 mmol), and the mixture was stirred at 100 C for 24 h. After being cooled to room temperature, the resulting solution was subjected to a short pad of silica gel using hexanes as an eluent. The filtrate was concentrated in vacuo to give the crude materials, which was purified by silica gel column chromatography to provide the corresponding compound 4j (0.13 g, 0.48 mmol) in 96% yield as an yellow oil.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 18599-22-9, its application will become more common.

Reference:
Article; Tamamoto, Ken; Yamada, Shigeyuki; Konno, Tsutomu; Beilstein Journal of Organic Chemistry; vol. 14; (2018); p. 2375 – 2383;,
Bromide – Wikipedia,
bromide – Wiktionary

Adding a certain compound to certain chemical reactions, such as: 327-52-6, name is 1-Bromo-2,4,5-trifluorobenzene, 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 327-52-6, Quality Control of 1-Bromo-2,4,5-trifluorobenzene

Into a 100 mL three-necked flask were added 4.62 g 1-bromo-2,4,5-trifluorobenzene (0.022 mol) and anhydrous tetrahydrofuran (50 mL). The resulting mixture was cooled to -20 C. The solution of isopropylmagnesium bromide (22 mmol) in tetrahydrofuran (22 ml, 1M THF) was slowly added dropwise under nitrogen. After the addition was complete, the reactants were maintained at -20 C. for later use. Cuprous bromide-dimethyl sulfide (0.41 g, 0.002 mol) was suspended in 5 ml anhydrous tetrahydrofuran. The resulting mixture was cooled to -5 C. The Grignard reagent as described above was slowly added dropwise under nitrogen. After 15 min, a solution of the aziridine compound as shown in the above reaction formula (4.16 g, 0.015 mol) in 30 mL tetrahydrofuran was slowly added dropwise. After additional 5 min, 50 mL saturated solution of ammonia chloride was added to quench the reaction. Into this obtained solution was added 50 mL ethyl acetate. The separated water layer was extracted with another 50 mL ethyl acetate. The obtained organic layers were collected together and further washed with saturated solution of sodium chloride and then dried over anhydrous sodium sulfate, followed by filtration and concentration to obtain a crude product, which was further treated by column chromatography to obtain a compound (4.08 g, 0.0116 mol, yield 77%). 1H NMR (400 MHz, CDCl3) delta7.537.22 (m, 10H), 7.05 (t, J=10.5 Hz, 1H), 6.93 (t, J=10.7 Hz, 1H), 5.12 (d, J=12.6 Hz, 1H), 3.973.85 (m, 1H), 3.82 (d, J=6.2 Hz, 1H), 3.773.55 (m, 1H), 3.62 (s, 2H), 3.51 (s, 2H), 2.82 (s, 2H), 1.871.68 (m, 1H), 1.631.48 (m, 1H). Ms (M++1): 400.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-2,4,5-trifluorobenzene, and friends who are interested can also refer to it.

Reference:
Patent; ZHEJIANG HISOAR PHARMACEUTICAL CO., LTD.; Pan, Xianhua; Li, Weijin; Zhang, Qunhui; Ruan, Libo; Yu, Wansheng; Deng, Fei; Ma, Tianhua; Huang, Mingwang; He, Minhuan; US2013/281695; (2013); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

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. 327-51-5, name is 1,4-Dibromo-2,5-difluorobenzene, This compound has unique chemical properties. The synthetic route is as follows., COA of Formula: C6H2Br2F2

The compound 2,5-difluoro-1,4-dibromobenzene (2 g, 7.40 mmol) was sequentially added to a 100 mL single-necked flask, (4.7 g, 18.52 mmol), potassium acetate (4 g, 44.40 mmol), Pd(dppf)Cl2 (210 mg, 0.287 mmol) and 1,4-dioxane (25 mL) The temperature was raised to 80 under reflux for 24h. Stop the reaction and cool, the reaction solution was washed with saturated brine 4 times, extracted with DCM twice, the combined organic phase, Dried over anhydrous MgSO4 overnight, filtered and the organic solvent was spun off. The crude product was extracted with PE-DCM (v / v, 2/1) as eluent, and then recrystallized from n-hexane to give 2 g of white needle-like crystals, Yield: 74.1%

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; Changzhou University; Liu Yu; Liu Yajun; Zhu Weiguo; Wang Yafei; (26 pag.)CN107400147; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 7073-94-1,Some common heterocyclic compound, 7073-94-1, name is 1-Bromo-2-isopropylbenzene, molecular formula is C9H11Br, 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: The bromobenzene (1 equiv) and (3-formylphenyl)boronic acid (1 equiv) were dissolved in a mixture of 1M sodium carbonate solution (15 mL), EtOH (5 mL) and toluene 15 mL). After nitrogen substitution, Pd(PPh3)4 (0.05 equiv) wasadded. The reaction mixture was stirred at 80 C under nitrogen atmosphere for 12 h. The reaction mixture was cooled, and wate r(15 mL) was added. The mixture was diluted with ethyl acetate(15 mL), and the insoluble material was filtered off through Celite. The organic layer of the filtrate was washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was purified by column chromatography using a mixture of petroleum ether/ethyl acetate (10:1, v/v) as eluent to afford the desired product as a solid.

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-isopropylbenzene, its application will become more common.

Reference:
Article; Li; Liu, Chunxia; Yang, Jianyong; Zhou; Ye, Zhiwen; Feng; Yue, Na; Tong; Huang, Wenlong; Qian, Hai; European Journal of Medicinal Chemistry; vol. 179; (2019); p. 608 – 622;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 133739-70-5, A common heterocyclic compound, 133739-70-5, name is 1-Bromo-2,3,5-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.

A mixture of 17.28 g of methyl (3R,4R)-4-[3-oxo-3-(6-methoxyquinolin-4-yl)propyl]-1-(prop-2-ynyl)-piperidine-3-carboxylate in 173 cm3 of triethylamine is stirred for 5 minutes under an inert atmosphere at a temperature in the region of 20 C. 4.05 g of tetrakis(triphenylphosphine)palladium, 0.834 g of cuprous iodide and 7.9 g of 1-bromo-2,3,5-trifluorobenzene are added.The mixture is stirred for 2 hours at a temperature in the region of 80 C. After cooling to approximately 20 C., 150 cm3 of ethyl acetate and 150 cm3 of water are added to the reaction mixture, which is then separated after settling out.The aqueous phase is extracted with 3 times 150 cm3 of ethyl acetate.The organic phases are pooled, washed with 5 times 150 cm3 of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure (5 KPa) at a temperature in the region of 40 C. The residue obtained is purified by chromatography under a nitrogen pressure of 50 KPa, on a column of silica gel (particle size 20-45mu; diameter 7 cm; 600 g), eluding with pure ethyl acetate and collecting first a fraction of 2.5 1, and then fractions of 250 cm3.Fractions 2 to 29 are pooled and then concentrated as above. 18.4 g of methyl (3R,4R)-4-[3-oxo-3-(6-methoxyquinolin-4-yl)propyl]-1-[3-(2,3,5-trifluorophenyl)prop-2-ynyl]-piperidine-3-carboxylate, in the form of a yellow oil, are obtained. [0293] 1H NMR spectrum (400 MHz, (CD3)2SO d6, delta in ppm): from 1.55 to 1.95 (mt: 5H); 2.39 (mt: 1H); 2.58 (broad d, J=10 Hz: 1H); 2.68 (mt: 1H); 2.82 (mt: 1H); 2.91 (mt: 1H); 3.09 (mt: 1H); 3.23 (mt: 1H); 3.58 (s: 3H); 3.61 (s: 2H); 3.88 (s: 3H); 7.31 (mt: 1H); 7.49 (dd, J=9 and 2.5 Hz: 1H); from 7.55 to 7.65 (mt: 1H); 7.73 (d, J=2.5 Hz: H); 7.92 (d, J=4.5 Hz: 1H); 8.02 (d, J=9 Hz: 1H); 8.89 (d, J=4.5 Hz: 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; Bacque, Eric; Bigot, Antony; Ahmad, Youssef Ei; Malleron, Jean-Luc; Mignani, Serge; Ronan, Baptiste; Tabart, Michel; Viviani, Fabrice; US2004/87619; (2004); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

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. 328-70-1, name is 1-Bromo-3,5-bis(trifluoromethyl)benzene, This compound has unique chemical properties. The synthetic route is as follows., Quality Control of 1-Bromo-3,5-bis(trifluoromethyl)benzene

10 g of 3,5-bis(trifluoromethyl)bromobenzene are mixed with 11 ml of cyclohexyldimethylamine and 30 ml of dimethylacetamide and degassed. 38 mg of palladium acetate and 152 mg of di(tert-butyl)phenylphosphine are dissolved in 5 ml of dimethylacetamide and added to the mixture. The mixture is transferred to an autoclave and 30 bar of ethylene are injected. The mixture is then heated to 110 C. and stirred at this temperature for 3 hours. At the end of the reaction, the mixture is cooled and the pressure released. Subsequently, 8.3 g of 1,5-dimethyl-3-trifluoromethyl-1H-pyrazole are added to the reaction mixture and the mixture is heated to 130 C. for 12 h. Afterwards, the mixture is cooled, added to water and worked up with toluene. Yield over the two steps: 10.5 g (76%) of slightly brownish solid.

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 328-70-1.

Reference:
Patent; Ebenbeck, Wolfgang; Rampf, Florian; Marhold, Albrecht; US2004/142820; (2004); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 54962-75-3,Some common heterocyclic compound, 54962-75-3, name is 3-Bromo-5-(trifluoromethyl)aniline, molecular formula is C7H5BrF3N, 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 3-amino-5-bromo-benzotrifluoride (1.0 g) in degassed (argon) tetrahydrofuran (2 mL) is added bis-(tri-o-tolylphosphino)palladium (0.15 g), a solution of dimethylamine in tetra-hydrofuran (2M, 4.2 mL), and a solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (1M, 10.4 mL). The reaction mixture is heated in a sealed vessel to 100C for approximately 2.5 hours to complete the reaction. The mixture is then cooled to room temperature, quenched by addition of water, and diluted with ethyl acetate. The product is extracted three times into 5% aqueous hydrochloric acid, and pooled acidic extracts are then basified with cooling by addition of 5N aqueous sodium hydroxide. This basic solution is then extracted with ethyl acetate, and these pooled organic extracts are washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting residue is chromatographed over silica gel (20-30% ethyl acetate in hexanes is used as the eluant) to provide the desired product as a slightly tinted solid.

The synthetic route of 54962-75-3 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Wyeth; EP1137645; (2004); B1;,
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 626-88-0 as follows. category: bromides-buliding-blocks

Example 271 N-(1H-5-Indazolyl)-N-[1-(4-methylpentyl)-4-piperidyl]amine 4-Piperidone hydrochloride monohydrate (768 mg) and potassium carbonate (1.38 g) were dissolved in anhydrous N,N-dimethylformamide (10 ml), and 1-bromo-4-methylpentane (603 mg) was added dropwise to the solution at room temperature. The reaction solution was stirred at room temperature for 18 hr. Ethyl acetate was then added thereto, and the mixture was washed with water and saturated brine and was dried over anhydrous sodium sulfate. The organic layer was concentrated under the reduced pressure to give an intermediate. This intermediate (766 mg) was dissolved in titanium tetraisopropoxide (3.8 ml). 5-Aminoindazole (445 mg) was added to the solution, and the mixture was stirred at room temperature for 18 hr. Methanol (3.8 ml) and sodium borohydride (79 mg) were added to the reaction solution, and the mixture was stirred for 18 hr. The reaction solution was diluted with ethyl acetate (40 ml), and a minor amount of water was added thereto, and the mixture was then filtered under the reduced pressure. The filtrate was concentrated under the reduced pressure, and the residue was purified by column chromatography on silica gel [chloroform/methanol] to give the title compound (200 mg, yield 13.3%). 1H-NMR (CDCl3, 400 MHz): 0.89 (d, J = 6.6 Hz, 6H), 1.15 – 1.26 (m, 2H), 1.49 – 1.59 (m, 5H), 2.07 – 2.23 (m, 1H), 2.35 – 2.39 (m, 2H), 2.90 – 3.00 (m, 2H), 3.29 – 3.38 (m, 1H), 6.80 – 6.82 (m, 2H), 7.26 (s, 1H), 7.88 (s, 1H) Mass spectrum (ESI-MS, m/z): 301 (M++1), 299 (M+-1)

According to the analysis of related databases, 626-88-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; KIRIN BEER KABUSHIKI KAISHA; EP1256574; (2002); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

698-19-1, name is 1-(2-Bromophenyl)-N-methylmethanamine, 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. Product Details of 698-19-1

General procedure: To an oven dried Schlenk tube, were added amine 2 (1 mmol) and alkyl (ethyl or methyl or tert-butyl) acrylate (5 mmol) at room temperature under nitrogen atmosphere. The reaction mixture was stirred at 110 C in an oil bath, for 24 h (in case of methyl as well as ethyl acrylates) and for 48 h (in case of tert-butyl acrylate). Progress of the Michael addition was monitored by TLC. The reaction mixture was allowed to attain room temperature, and excess of alkyl acrylate was removed under vacuum (10-2 mbar). To the resultant reaction intermediate (i.e., Michael addition product 3) at room temperature, were added Pd(OAc)2 (10 mol %), PPh3 (20 mol %), and Cs2CO3 (2 mmol) followed by toluene (3 mL) under nitrogen atmosphere. The reaction mixture was then allowed to stir at 80 C for 24 h (in case of 4a-c and 4f), 36 h (in case of 4d, 4e, 4g, 4i, 4j and 4l-n), and 48 h (in case of 4h and 4k) in an oil bath and the progress was monitored by TLC. The mixture was cooled to room temperature, treated with aqueous NH4Cl solution and then extracted with ethyl acetate (3×15 mL). The organic layer was washed with saturated NaCl solution, dried (Na2SO4), and filtered. Evaporation of the solvent under reduced pressure and purification of the crude material by silica gel column chromatography (petroleum ether/ethyl acetate) furnished the tetrahydroisoquinoline 4 (70-85%).

The synthetic route of 698-19-1 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Reddy, Alavala Gopi Krishna; Satyanarayana, Gedu; Tetrahedron; vol. 68; 38; (2012); p. 8003 – 8010;,
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. 38573-88-5, name is 1-Bromo-2,3-difluorobenzene, A new synthetic method of this compound is introduced below., category: bromides-buliding-blocks

In a 3 L four-necked flask purged with nitrogen, 148.3 g of 4-pentylphenylboronic acid, 102 g of 1-bromo-2,3-difluorobenzene, 5.56 g of tetrakistriphenylphosphine palladium (0) complex and 270 g of hydrogen carbonate Sodium and 750 ml of N, N-dimethylacetamide were added, and the mixture was stirred at 100 ° C. for 8 hours. The completion of the reaction was confirmed with a gas chromatograph (GC), and the system was cooled to room temperature. 1 L of water was added to the reaction system and stirring was carried out, 1 L of heptane was added thereto, and the mixture was vigorously stirred. The organic layer was separated and then extracted twice with 1 L of heptane. After washing the obtained heptane solution twice with 300 ml of water, the solvent was distilled off, and purification was carried out using 250 g of silica gel using heptane as a solvent, to obtain 100 g of the desired product as a colorless transparent liquid . Yield 72.8percent. GC purity 97.7percent. M + 260.

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; DIC CORPORATION; KUSUMOTO, TETSUO; AOKI, YOSHIO; (47 pag.)JP6136589; (2017); B2;,
Bromide – Wikipedia,
bromide – Wiktionary