Tag: M.W=200-300

Reference of 103273-01-4, A common heterocyclic compound, 103273-01-4, name is 2-Bromo-4-(tert-butyl)aniline, molecular formula is C10H14BrN, 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.

To a mixture of 2-bromo-4- tert-butylaniline (Compound 1-1, 16.8 g, 74 mmol) and CuCN (13.29 g, 148 mmol) in a 250 mL round-bottom flask was added NMP (N-methylpyrrolidone, 100 mL) . The mixture was heated to reflux under nitrogen until TLC analysis showed full conversion of the starting material. The mixture was cooled to room temperature and the solvent was removed under vacuum. To the residue was added aq. NH40H at 0 C. Ethyl acetate was used for extraction (three times) . The combined organic phase was dried over anhydrous MgSC>4, filtered, and evaporated under vacuum. The residue was purified by flash chromatography (ethyl acetate : hexanes = 1:10) to provide the aminobenzonitrile Compound 1-2 as a yellow solid (10.8 g, 84% yield) . 1H NMR (400 MHz, CDC13) delta 7.39- 7.33 (m, 2H) , 6.70 (d, J = 8.4 Hz, 1H) , 4.32 (br, 2H, NH2), 1.25 (s, 9H) ; 13C NMR (100 MHz, CDC13) delta 147.48, 141.15, 131.77, 128.56, 118.22, 115.32, 95.63, 34.02, 31.21. HRMS (ESI-TOF) m/z Calcd for C11H15N2+ [M+H] + 175.1230, found 175.1235.

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; THE SCRIPPS RESEARCH INSTITUTE; YU, Jin-Quan; (107 pag.)WO2016/123361; (2016); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 33070-32-5, These common heterocyclic compound, 33070-32-5, name is 5-Bromo-2,2-difluorobenzodioxole, 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.

EXAMPLE 89E 2.2-difluoro-1,3-benzodioxol-5-ylboronic acid A solution of 5-bromo-2,2-difluorobenzodioxole (1.18 g, 4.97 mmol) in anhydrous diethyl ether (8 mL) at -78 C. was treated with 2.5M n-BuLi in hexane (2.4 mL, 5.97 mmol), stirred for 1 hour, and treated with triisopropyl borate (1.5 mL, 6.46 mmol). The mixture was slowly warmed to room temperature and stirred for about 18 hours. The reaction was quenched with saturated NH4Cl/10% HCl and extracted with ethyl acetate. The combined extracts were dried (MgSO4), filtered, and concentrated. The concentrate was used directly without further purification. 1H NMR (CD3OD) delta 7.26-7.11 (m, 3H).

Statistics shows that 5-Bromo-2,2-difluorobenzodioxole is playing an increasingly important role. we look forward to future research findings about 33070-32-5.

Reference:
Patent; Claiborne, Akiyo K.; Gwaltney, II, Stephen L.; Hasvold, Lisa A.; Li, Qun; Li, Tongmei; Lin, Nan-Horng; Mantei, Robert A.; Rockway, Todd W.; Sham, Hing L.; Sullivan, Gerard M.; Tong, Yunsong; Wang, Gary; Wang, Le; Wang, Xilu; Wang, Wei-Bo; US2002/115640; (2002); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 142808-15-9, 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. 142808-15-9 name is 4-Bromo-2-fluorobenzotrifluoride, 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.

Into a 50 mL dry, round bottom flask fitted with a magnetic stirring bar, a dropping funnel (25 mL) and a refluxing condenser was placed magnesium turnings (129 mg, 5.3 mmol) and anhydrous diethyl ether (4 mL). Anhydrous diethyl ether (16 mL) was added to the dropping funnel followed by 4-bromo- 2-fluoro-1-(trifluoromethyl)benzene (1.17 g, 4.8 mmol). A portion of the 4- bromo-2-fluoro-1-(trifluoromethyl)benzene solution (2 mL) as well as iodine (5 mg) was added to the flask which was then heated to reflux and stirred. Heating was stopped and the remainder of the 4-bromo-2-fluoro-1- (trifluoromethyl)benzene solution was added dropwise to the flask at such a rate that the solvent refluxed gently (about 10 minutes). After the addition was complete, the reaction was heated to reflux for 2 hours. The mixture was cooled to -78 C and a solution of 2-(2,6,6-trimethylcyclohex-1- enyl)acetaldehyde (200 mg, 1.2 mmol) in diethyl ether (3 mL) was added dropwise via syringe. The reaction was allowed to warm to room temperature and stirred for 4 hours. The reaction was quenched by addition of saturated aqueous ammonium chloride (10 mL). The mixture was diluted with water (20 mL) and the organics were extracted with diethyl ether (30 mL x 2). The combined organic phase was washed with brine (60 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: petroleumether/ethyl acetate = 100/1 ) to afford the title compound as a yellow oil (138 mg, Yield: 35%). Rf = 0.6 (10:1 petroleum ether/ethyl acetate); 1H NMR (400 MHz, CDCI3) delta 7.57 (t, J = 7.6 Hz, 1 H), 7.30-7.23 (m, 2H), 4.89 (t, J = 7.4 Hz, 1 H), 2.48-2.46 (m, 2H), 2.22 (d, J = 1 .2 Hz, 1 H), 2.12-1.96 (m, 2H), 1.68 (s, 3H), 1 .68-1 .62 (m, 2H), 1 .51 -1 .48 (m, 2H), 1 .07 (s, 3H), 1.06 (s, 3H) ppm; Mass spectrum (ESI +ve) m/z 331 (M + H+).

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

Reference:
Patent; BIKAM PHARMACEUTICALS, INC.; QUACH, Tan; BERMAN, Judd; GARVEY, David, S.; WO2013/81642; (2013); A1;,
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. 33070-32-5, name is 5-Bromo-2,2-difluorobenzodioxole, A new synthetic method of this compound is introduced below., name: 5-Bromo-2,2-difluorobenzodioxole

Step 1: (S)-Methyl2-(tert-butoxycarbonyl)-3-(2,2-difluorobenzo[d][1,3]dioxol-5-yl) propanoate To a 25 mL RBF was added zinc powder (1.03 g, 15.8 mmol) and iodine (0.0161 g, 0.0633 mmol). The mixture was heated with a heat gun for 5 minutes and the resulting mixture was then flushed with nitrogen 3 times and allowed to cool to rt. A solution of (R)-methyl2-(tert-butoxycarbonyl)-3-iodopropanoate (3.47 g, 10.5 mmol) in 5 mL of DMF was added dropwise to the mixture over 3 minutes and the resulting grey slurry was stirred at 0 C. for 20 minutes before being warmed to rt. After stirring at rt for 30 minutes, 5-bromo-2,2-difluorobenzo[d][1,3]dioxole (2.50 g, 10.5 mmol), Pd2(dba)3 (0.193 g, 0.211 mmol) and S(Phos) (0.346 g, 0.844 mmol) were added and the reaction mixture was heated to 40 C. for 2 hours. The resulting mixture was cooled to rt and partitioned between ethyl acetate (50 mL) and a solution of ~9:1 saturated ammonium chloride/ammonium hydroxide pH=9 (250 mL). The aqueous layer was extracted with ethyl acetate (3*100 mL) and the combined organic layers were washed with water, brine, and dried over sodium sulfate. Concentration of the filtered solvents and purification of resulting crude material by silica gel chromatography provided (S)-methyl 2-(tert-butoxycarbonyl)-3-(2,2-difluorobenzo[d][1,3]dioxol-5-yl)propanoate (1.89 g, 49.9% yield) as a slightly brown oil.

The synthetic route of 33070-32-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Amgen Inc.; US2010/120774; (2010); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 13194-73-5,Some common heterocyclic compound, 13194-73-5, name is 3,5-Dibromo-4-methylaniline, molecular formula is C7H7Br2N, 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 round-bottom flask were added sulfoacetic acid (0.14g, 1.0 mmol), DMF (5 mL), HBTU (0.379g, 1 mmol), 3,5-dibromo-4- methylaniline (0.265g, 1 mmol), DIEA (0.52 mL, 3 mmol), and DMAP (0.012g, 0.1 mmol). The mixture was stirred at room temperature for 2 hours, and then it was subjected to reversed- phase HPLC purification to give product L335-M34 as a white solid (0.385g, 99% yield): 1H NMR (500 MHz, DMSO) delta 10.08 (s, 1H), 7.87 (s, 2H), 3.52 (s, 2H), 2.42 (s, 3H); 13C NMR (DMSO) delta 164.6, 138.9, 130.5, 124.1, 121.8, 59.1, 22.6; ESI-HRMS calcd for (M + H+) 385.8692, found 385.8696

The synthetic route of 13194-73-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; INDIANA UNIVERSITY RESEARCH & TECHNOLOGY CORPORATION; ZHANG, Zhong-Yin; HE, Rongjun; (128 pag.)WO2016/196591; (2016); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 149910-98-5,Some common heterocyclic compound, 149910-98-5, name is 7-Bromoisochroman, molecular formula is C9H9BrO, 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: 4.1. General procedure for the CDC reaction of benzylic ethers with carbonyl compounds To a solution of 1 or 4 (0.25mmol, 1equiv), 2 (1.25 mmol, 5 equiv) and CuBr2 (0.05 mmol, 0.2 equiv) was added Na2S2O8 (0.75 mmol, 3 equiv). Then the mixture was stirred at 80C until the starting material disappeared monitored by TLC. After that, the above mixture was directly purified by flash chromatography (ethyl acetate/petroleum ether as eluent) to give the desired product 3 or 5.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 7-Bromoisochroman, its application will become more common.

Reference:
Article; Pan, Xinhui; Hu, Qingwen; Chen, Wenfang; Liu, Xigong; Sun, Bin; Huang, Zhouli; Zeng, Ziyu; Wang, Liguo; Zhao, Dan; Ji, Mei; Liu, Lei; Lou, Hongxiang; Tetrahedron; vol. 70; 21; (2014); p. 3447 – 3451;,
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. 113170-72-2, name is 3-Bromo-5-(trifluoromethyl)benzene-1,2-diamine, This compound has unique chemical properties. The synthetic route is as follows., HPLC of Formula: C7H6BrF3N2

Example 21b 0.2 mol of 3-bromo-5-trifluoromethyl-phenylene-diamine were heated with 150 ml of trifluoroacetic acid at reflux temperature for 3 hours. For working up, excess trifluoroacetic acid was distilled off and the residue was partitioned between 100 ml of water and 300 ml of ethyl acetate. The organic phase was separated off, washed successively with in each case 100 ml of aqueous sodium hydrogen carbonate solution and water, dried over sodium sulphate, and concentrated in vacuo. The residue was purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:1). 4-Bromo-6-trifluoromethyl-2-trifluoromethyl-1H-benzimidazole with a melting point of 149-151 C. was obtained.

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 113170-72-2.

Reference:
Patent; Bayer Aktiengesellschaft; US5877195; (1999); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 138526-69-9, 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. 138526-69-9, name is 1-Bromo-3,4,5-trifluorobenzene, This compound has unique chemical properties. The synthetic route is as follows.

Addition of iodine to a mixture of magnesium (264 mg, 11.0 mmol) and THF (5 mL)(5.0 mg) and 5-bromo-1,2,3-trifluorobenzene in THF (0.5 mL)(211 mg, 1 mmol) solution. The mixture is heated to 60 C,And 5-bromo-1,2,3-trifluorobenzene added dropwise in THF (4.5 mL)(1.9 g, 9 mmol) solution. The reaction is heated for two hours,The solution was cooled to room temperature and used directly in the next step.

The chemical industry reduces the impact on the environment during synthesis 1-Bromo-3,4,5-trifluorobenzene. I believe this compound will play a more active role in future production and life.

Reference:
Patent; PFIZER INC.; KUMPF, ROBERT ARNOLD; MCALPINE, INDRAWAN JAMES; MCTIGUE, MICHELE ANN; PATMAN, RYAN; RUI, EUGENE YUANJIN; TATLOCK, JOHN HOWARD; TRAN-DUBE, MICHELLE BICH; WYTHES, MARTIN JAMES; (445 pag.)TW2018/2074; (2018); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Synthetic Route of 454-79-5, 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 454-79-5 as follows.

Under ice-cooling, 2.6 mL of diethyldisulfide was dropped to a mixture of 5.0 g of 2-bromo-5- (trifluoromethyl) aniline, 2.77 mL of isoamyl nitrite and 50 mL of acetonitrile. The reaction mixture was stirred at 50 C. for 6 hours. The reaction mixture was allowed to cool to room temperature, water was added and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 4.5 g of Intermediate 1-13 shown below.

According to the analysis of related databases, 454-79-5, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Sumitomo Chemical Co., Ltd.; Murakami, Shin’ichirou; (398 pag.)JP2019/94335; (2019); A;,
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, Recommanded Product: 327-52-6

13.2g metal magnesium and 400ml tetrahydrofuran were added into a clean flask. 116.05g trifluorobromobenzene was added thereto dropwisely after initiation by iodine and the reaction was kept at 30-40C for 3 hours for use. 29.9g (S)-methyl 3-(tert-butoxycarbonyl amino)-4-oxo-n-butyrate was dissolved in 300ml THF, and cooled to -20 C. The solution mentioned above was added thereto dropwisely over two hours and kept at the temperature for 3 hours. 400ml ammonium chloride solution was added dropwisely. Layers were separated. The aqueous layer was extracted with tetrahydrofuran. The organic layer was dried and concentrated to get 14.5g (3S)-methyl 3-(tert-butoxy carbonylamino)-4-hydroxy-4-(2,4,5-trifluoromethyl-phenyl)butyrate (yield: 66%).

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, 1-Bromo-2,4,5-trifluorobenzene, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Zhejiang Jiuzhou Pharmaceutical Co., Ltd.; EP2481722; (2012); A1;,
Bromide – Wikipedia,
bromide – Wiktionary