Category: bromides-buliding-blocks

Electric Literature 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

Adding a certain compound to certain chemical reactions, such as: 7051-34-5, name is (Bromomethyl)cyclopropane, 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 7051-34-5, Application In Synthesis of (Bromomethyl)cyclopropane

Cyclopropyl methyl bromide (1.4 ml, 14.46 mmol), sodium iodide (0.986 g, 6.6 mmol) and potassium carbonate (3.64 g, 26.3 mmol) were added sequentially to a stirred solution of 4-hydroxybenzoic acid methyl ester (2.0 g, 13.14 mmol), in 25 ml of acetone at room temperature and the mixture was refluxed for 44 h. The solvent was evaporated to obtain a residue to which 10% NaOH (80 ml) was added. The solution was extracted with DCM twice. The combined DCM layers were washed with water and brine and dried over anhydrous Na2SO^ The solvent was evaporated to obtain 2.5 g (92.25%) of 4- cyclopropylmethoxybenzoic acid methyl ester. LCMS: [M+H]+ 270.3; IH-NMR (CDCl3): 7.964-7.986 (d, 2H, J=8.8 Hz), 6.895-6.917 (d, 2H, J=8.8 Hz), 3.879 (s, 3H), 3.849-3.867 (d, 2H, J=7.2 Hz), 1.262-1.281 (m, IH), 0.639-0.671 (m, 2H), 0.360-0.372 (m, 2H).

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:
Patent; FOREST LABORATORIES HOLDINGS LIMITED; SARMA, Pakala, Kumara Savithru; ACHARYA, Vinod, Parameshwaran; KASIBHATLA, Srinivas, Rao; VISWANADHAN, Vellarkad, Narayana; SHEKHAR, Polisetti; BISCHOFF, Alexander; WO2010/127212; (2010); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Related Products of 1559-88-2, A common heterocyclic compound, 1559-88-2, name is 3-Bromo-1,2,4,5-tetrafluorobenzene, molecular formula is C6HBrF4, 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 15 Air inside a reaction vessel of the same type as the one used in Example 1 was replaced with a nitrogen gas in a satisfactory manner, after which 20 ml of a t-butyl methyl ether solution containing 0.0199 mol of suspended n-propyl magnesium bromide was charged to the reaction vessel. Meanwhile, 0.0183 mol of 1-bromo-2,3,5,6-tetrafluorobenzene was charged to the dropping funnel as the fluoroaryl halide. Then, 1-bromo-2,3,5,6-tetrafluorobenzene in the dropping funnel was dropped to the reaction vessel over 20 minutes at room temperature, and the reaction solution was stirred for 4 hours at room temperature. Consequently, 2,3,5,6-tetrafluorophenyl magnesium bromide was obtained in the form of a colorless t-butyl methyl ether solution.

The synthetic route of 1559-88-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Nippon Shokubai Co., Ltd.; US6235222; (2001); B1;,
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. 348-57-2, name is 1-Bromo-2,4-difluorobenzene, This compound has unique chemical properties. The synthetic route is as follows., category: bromides-buliding-blocks

To a suspension of l-bromo-2,4-difluorobenzene (lOg, 52.1mmol, l.Oeq) in cold H2SO4 (37.9mL) was added Conc.HN03 (33.3mL) in a dropwise manner keeping the internal temp 20°C, stirred for 10 min at 0°C then, the reaction mixture was poured into a mixture of diethyl ether (250mL) and ice water (250mL) with vigorous stirring. The organic layer was separated and the aqueous layer was again extracted with Et20 (250mL). The combined organic layer was washed with Satd. sodium bicarbonate (2 X 200 mL) followed by satd. brine (2 X 200 mL) solution. The separated organic layer was dried over Na2S04 and concentrated under reduced pressure to give crude product which was purified by column chromatography (SiO 100-200 mesh) using 15percent EtOAc in pet ether as an eluent to give l-bromo-2,4-difluoro-5 -nitrobenzene (52g, 72percent yield) as a yellow color liquid. LCMS: M+H]+ 272.23.

According to the analysis of related databases, 348-57-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; ONTARIO INSTITUTE FOR CANCER RESEARCH (OICR); AL-AWAR, Rima; ZEPEDA-VELAZQUEZ, Carlos Armando; PODA, Gennady; ISAAC, Methvin; UEHLING, David; WILSON, Brian; JOSEPH, Babu; LIU, Yong; SUBRAMANIAN, Pandiaraju; MAMAI, Ahmed; PRAKESCH, Michael; STILLE, Julia Kathleen; (1053 pag.)WO2017/147700; (2017); 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., Recommanded Product: 33070-32-5

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

These common heterocyclic compound, 21865-50-9, name is 6-Bromo-2,3,4,9-tetrahydro-1H-carbazole, 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. Formula: C12H12BrN

In a 1 L round-bottom flask, 60.0 g (0.240 mol) of synthesized in [Scheme 2], 73.4 g (0.360 mol) of iobenzene, 2.3 g (0.012 mol) of copper iodide (CuI),Tripotassium phosphate (K3PO4) 106.96 g (0.504 mol),54.8 g (0.480 mol) of trans-1,2-cyclohexanediamineAnd 300.0 ml of 1,4-dioxane was added and refluxed for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with 1 L of water, and the organic layer was anhydrous and concentrated under reduced pressure. Then, 72.0 g (yield 92.0%) of was obtained by using an adsorption column chromatography.

The synthetic route of 6-Bromo-2,3,4,9-tetrahydro-1H-carbazole has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SFC Ltd.; Kim Si-in; Kim Nam-i; (52 pag.)KR102017507; (2019); B1;,
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

Electric Literature 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

Application 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

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. 58534-95-5, name is 3-Bromo-2-fluoroaniline, This compound has unique chemical properties. The synthetic route is as follows., Recommanded Product: 3-Bromo-2-fluoroaniline

A mixture of 2,2,2-Trichloroethane-1,1-diol (8.09 g, 49.33 mmol) and Na2SO4 (53 g, 370 mol) were dissolved in water and warmed to 35C. 3-bromo-2- fluorobenzenamine (7.77 g, 41.11 mmol) in water was added, followed by 35% aqueous HC1 (4.6 mL) and hydroxylamine hydrochloride (9.08 g, 131.6 mol). The resultingmixture was heated to 90C for 16 h and yellow precipitate was formed. The mixture was cooled to room temperature, the solid was filtered, washed with water, and dried in the air to afford the desired product (6.5 g, 61% yield)

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 58534-95-5.

Reference:
Patent; ARAXES PHARMA LLC; LI, Liansheng; FENG, Jun; LONG, Yun Oliver; LIU, Yuan; WU, Tao; REN, Pingda; LIU, Yi; (246 pag.)WO2017/87528; (2017); A1;,
Bromide – Wikipedia,
bromide – Wiktionary