Category: bromides-buliding-blocks

A common heterocyclic compound, 1422-53-3, name is 2-Bromo-4-fluorotoluene, molecular formula is C7H6BrF, 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. 1422-53-3.

a) Preparation of 2-Bromo-1-(Bromomethyl)-4-Fluorobenzene A mixture of 2-Bromo-4-Fluorotoluene (46.6 g, 0.25 mol, Aldrich), N-bromosuccinimide (46.3 g, 0.26 mol, Aldrich) and benzoyl peroxide (0.5 g, 0.002 mol, Aldrich) in carbon tetrachloride (500 ml) was refluxed and illuminated (250 watt, infrared lamp) for 18 h. After cooling to room temperature, the succinimide was filtered and the filtrate was concentrated in vacuo. Chromatography on silica gel with hexanes as eluent gave 41.8 g (62%) of 2-bromo-1-(bromomethyl)-4-fluorobenzene as a white solid: mp 47-49 C.

The synthetic route of 2-Bromo-4-fluorotoluene has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Glaxo Wellcome Inc.; US5708033; (1998); A;,
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69321-60-4, name is 2,6-Dibromotoluene, 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. 69321-60-4

A 50-mL three-neck round-bottomed flask equipped with a reflux condenser, magnetic stirrer and nitrogen inlet was charged with ethyl l-(2-aminoethyl)-4, 5,6,7- tetrahydro-lH-indole-2-carboxylate 101k (560 m g, 2.95 mmol), 2,6-dibromotoluene (1.47 g, cesium carbonate (1.92 g, 5.90 mmol), N,N’-dimethylethylenediamine (260 mg, 2.95 mmol) and 1,4-dioxane (25 mL). After bubbling nitrogen through the resulting suspension for 30 min, copper N,N’-dimethylethylenediamine (260 mg, 2.95 mmol) was added, and the reaction mixture was heated at 105 C (oil bath temperature) for 14 h. After this time, the mixture was cooled to room temperature and filtered. The filtrate was diluted with ethyl acetate (100 mL) and water (20 mL). The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (3 x 30 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by columnchromatography to afford a 57% yield (600 mg) of 2-(3-bromo-2-methylphenyl)-3,4,6,7,8,9- hexahydropyrazino[l,2-fl]indol-l(2H)-one 1011 as a white solid: mp 163-165 C; ‘H NMR (500 MHz, DMSO-i? delta 7.57 (dd, 1H, J = 8.0, 0.5 Hz), 7.32 (d, 1H, J = 7.5 Hz), 7.21 (t, 1H, J = 8.0 Hz), 6.50 (s, 1H), 4.11 (m, 3H), 3.75 (m, 1H), 2.59 (m, 2H), 2.45 (m, 2H), 2.21 (s, 3H), 1.78 (m, 2H), 1.68 (m, 2H); (APCI+) m/z 358.6 (M+H)

Statistics shows that 69321-60-4 is playing an increasingly important role. we look forward to future research findings about 2,6-Dibromotoluene.

Reference:
Patent; GILEAD CONNECTICUT, INC.; GENENTECH, INC.; BARBOSA, Antonio, J., M.; BLOMGREN, Peter, A.; CURRIE, Kevin, S.; KRISHNAMOORTHY, Ravi; KROPF, Jeffrey, E.; LEE, Seung H.; MITCHELL, Scott A.; ORTWINE, Daniel; SCHMITT, Aaron, C.; WANG, Xiaojing; XU, Jianjun; YOUNG, Wendy; ZHANG, Honglu; ZHAO, Zhongdong; ZHICHKIN, Pavel E.; WO2011/140488; (2011); A1;,
Bromide – Wikipedia,
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A common compound: 1435-52-5, name is 1,4-Dibromo-2-fluorobenzene, 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. 1435-52-5

General procedure: 6.9 1,3-Di(4′-fluorphenyl)-5-fluorobenzene (7i): Starting with 6 (100 mg, 0.37 mmol), Cs2CO3 (263 mg, 0.81 mmol), Pd(PPh3)4 (3 molpercent), 4-fluoromethylphenylboronic acid (109 mg, 0.78 mmol) and 1,4-dioxane (4 mL), 7i was isolated as a colorless solid (54 mg, 48percent). Mp 145-149 ¡ãC. 1H NMR (300 MHz, CDCl3): delta = 7.03-7.09 (m, 2H, ArH), 7.24-7.29 (m, 1H, ArH), 7.32-7.36 (m, 4H, ArH), 7.41-7.50 (m, 4H, ArH). 13C NMR (75 MHz, CDCl3): delta = 114.5 (dd, J = 24.2, 3.8 Hz, CH), 115.5 (d, J = 21.5 Hz, CH), 115.9 (d, J = 21.4 Hz, CH), 122.8 (t, J = 3.2 Hz, CH), 128.2 (CH), 128.8 (CH), 129.2 (CH), 130.5 (d, J = 3.34 Hz, CH), 130.7 (dd, J = 8.2, 3.3 Hz, CH), 130.9 (d, J = 3.3 Hz, CH), 131.3 (CH), 133.7 (d, J = 1.1 Hz, C), 134.2 (d, J = 4.9 Hz, C), 137.8 (d, J = 1.7 Hz, C), 141.1 (d, J = 8.3 Hz, C), 159.9 (d, JCF = 248.2 Hz, CF), 162.5 (d, JCF = 247.6 Hz, CF), 168.8, (d, JCF = 247.7 Hz, CF). 19F NMR (282 MHz, CDCl3): delta = -114.2.5, -117.3, -117.6 (CF). IR (ATR, cm-1): , 3041 (w), 2953 (w), 2917 (w), 2849 (w), 1907 (w), 1602 (w), 1595 (w), 1524 (w), 1480 (m), 1429 (w), 1387 (w), 1298 (w), 1224 (m), 1163 (m), 1094 (w), 1006 (w), 967 (w), 892 (m), 833 (m), 809 (s), 751 (w), 709 (w), 690 (w), 613 (w), 577 (m), 546 (w). MS (EI, 70 eV); m/z (percent) = 284 (100) [M]+. HRMS (EI) calcd. for C18H11F3 [M]+: 284.08074; found 284.10827.

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, 1435-52-5, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Sharif, Muhammad; Maalik, Aneela; Reimann, Sebastian; Feist, Holger; Iqbal, Jamshed; Patonay, Tama?s; Villinger, Alexander; Langer, Peter; Journal of Fluorine Chemistry; vol. 146; (2013); p. 19 – 36;,
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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 399-94-0 as follows. 399-94-0

Under nitrogen, 2,5-difluorobromobenzene (15.05 g, 78 mmol) was dissolved in dry toluene (50 mL), the ice salt bath was cooled below -10 C,A solution of isopropylmagnesium chloride / lithium chloride tetrahydrofuran (66 mL, 1.3 mol / L) was added dropwise and the mixture was stirred at about -10 C for 1 hour.A solution of 1D (10 g, 39 mmol) in dry tetrahydrofuran (100 mL) was added dropwise to the reaction solution, maintaining the temperature at -10 C, and the reaction was carried out at room temperature for 4 hours.The temperature was lowered to about -10 C, saturated ammonium chloride solution (40 mL) was added dropwise, stirred for 10 minutes, adjusted to pH 5 to 6 with 3 mol / L hydrochloric acid solution,The aqueous phase was extracted with methyl tertiary butyl ether (50 mL x 2). The organic phases were combined, washed with saturated sodium chloride solution (30 mL x 2). The organic phase was dried over anhydrous sodium sulfate, filtered,Column chromatography (petroleum ether / ethyl acetate (v / v) = 50: 1-8: 1) gave a pale yellow solid 1E (10.1 g, yield 83.5%).

According to the analysis of related databases, 399-94-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Sichuan Haisco Pharmaceutical Co.,Ltd; FAN, JIANG; CHEN, QINGPING; JIANG, WEI; ZHENG, SUXIN; YE, FEI; (128 pag.)TW2017/8221; (2017); A;,
Bromide – Wikipedia,
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22034-13-5, 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. 22034-13-5, name is 4-Bromobenzo[c][1,2,5]thiadiazole, This compound has unique chemical properties. The synthetic route is as follows.

Step 1, preparation of 3-bromo-1,2-diaminobenzene, of which the equation is represented as follows: Specific preparation is described as follows: dissolving 4-bromo-2,1,3-benzothiadiazole (20 mmol) in ethanol solvent (180 ml), adding sodium borohydride (0.38 mmol) at 0¡ã C., then raising the temperature to room temperature, stirring for 24 hours, distilling organic solvent of reaction product, after adding water (200 ml), washing with saline water, then extracting with diethyl ether, drying with anhydrous sodium sulfate. Product is obtained after solvent is rotary dried. The test result is GC-MS (EI-m/z): 186 (M+).

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; Ocean’s King Lighting Science & Technology Co., Ltd.; Zhou, Mingjie; Huang, Jie; Huang, Jiale; US8822634; (2014); B2;,
Bromide – Wikipedia,
bromide – Wiktionary

33070-32-5, 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.

Step 1: Pre [00383] To a stirring solution of tert-butyllithium (1.76 mL, 3.0 mmol, 2.0 equiv, 1.7 M in pentane) at -78 C was added dropwise a solution of 5-bromo-2,2-difluorobenzo-[l ,3]- dioxole (355 mg, 1.5 mmol, 1.0 equiv) in THF (5 mL). After 30 min, ethyl formate (44 mg, 0.5 mmol, 0.33 equiv) in THF (1 mL) was added. The mixture was stirred at -78 C for 1 h and subsequently warmed to room temperature and stirred for an additional 4 h. The reaction mixture was quenched by the addition of a saturated solution of NH4C1 and extracted with EtOAc (3x). The organic layers were combined, dried over a2S04, and concentrated under reduced pressure. Purification of the crude oil by flash chromatography (15% EtOAc/hexanes) provided bis(2,2-difluorobenzo[d][l,3]dioxol-5-yl)methanol as an off-white solid (196 mg, 92%): ‘H NMR (400 MHz, CDC13) delta 7.09 (d, J= 1.61 Hz, 2H), 7.07 (dd, J= 1.74, 8.18 Hz, 2H), 7.02 (d, J= 8.15 Hz, 2H), 5.81 (d, J= 3.03 Hz, 1H), 2.28 (d, J= 3.27 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; ABIDE THERAPEUTICS; THE SCRIPPS RESEARCH INSTITUTE; CISAR, Justin, S.; GRICE, Cheryl, A.; JONES, Todd, K.; WANG, Dong-Hui; WEBER, Olivia; CRAVATT, Benjamin, F.; NIPHAKIS, Micah, J.; COGNETTA, Armand; CHANG, Jae Won; WO2013/142307; (2013); A1;,
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 5469-19-2 as follows. 5469-19-2

Preparation 1 d: 2-tert-Butyl 5-methyl 6-hromo-2,3-dibydro-1H-isoiiidole-2,5-dicarboxylateStep A: S-Brornobenzene-1,2,4-tricarboxylic acidBromotrimethyl benzene (40.7 g, 205 mmol) was added to a mixture of water (3.25 L), potassium permanganate (232 g, 1.468 mol) and sodium carbonate (28.5 g, 206 mmol). The mixture was stirred at reflux for 60 h. Ethanol (820 mE) was added dropwise, and theresultant mixture was filtered hot through celite, then allowed to cool to ambient temperature. The filtrate was acidified with concentrated aqueous HCI, and the organic solvent was removed in vacuo, The solid product was isolated by filtration.

According to the analysis of related databases, 5469-19-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; LES LABORATOIRES SERVIER; VERNALIS (R&D) LIMITED; DAVIDSON, James, Edward, Paul; MURRAY, James, Brooke; CHEN, I-Jen; WALMSLEY, Claire; DODSWORTH, Mark; MEISSNER, Johannes, W., G.; BROUGH, Paul; FEJES, Imre; TATAI, Janos; NYERGES, Miklos; KOTSCHY, Andras; SZLAVIK, Zoltan; GENESTE, Olivier; LE TIRAN, Arnaud; LE DIGUARHER, Thierry; HENLIN, Jean-Michel; STARCK, Jerome-Benoit; GUILLOUZIC, Anne-Francoise; DE NANTEUIL, Guillaume; WO2015/11164; (2015); A1;,
Bromide – Wikipedia,
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Some common heterocyclic compound, 766-46-1, name is 2′-Bromophenylacetylene, molecular formula is C8H5Br, 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. 766-46-1

For the synthesis of 1e, the title compound 1e? wasprepared as follows. A solution of LDA, prepared from iPr2NH(0.93 mL, 6.5 mmol) and nBuLi (2.7M in hexane, 2.4 mL, 6.5 mmol)in THF (6 mL) at 0 C, was added to a solution of 1-bromo-2-ethynylbenzene [766-46-1] (1.1 g, 5.9 mmol) in THF (6 mL)at 78 C for 30 min tert-Butyldimetylsilyl chloride [18162-48-6](1.1 g, 7.1 mmol) was added to the mixture at that temperature.The reaction mixturewas warmed to room temperature and stirredfor 12 h. After adding aqueous NH4Cl, the aqueous mixture wasextracted with hexane three times. The combined organic phasewas dried over Na2SO4 and evaporated. Purification of the residueby silica-gel column chromatography gave 1-bromo-2-[2-[(1,1-dimethylethyl)dimethyl-silyl]ethynyl]benzene in (1.6 g, 5.4 mmol,92%) as a pale yellow liquid. 1H NMR (400 MHz, CDCl3, 7.26 ppm)d 0.21 (s, 6H), 1.02 (s, 9H), 7.15 (ddd, J 7.6, 7.6, 1.6 Hz, 1H), 7.24(ddd, J 7.6, 7.6, 1.2 Hz, 1H), 7.50 (dd, J 7.6, 1.6 Hz, 1H), 7.57 (dd,J 8.0, 1.2 Hz, 1H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 766-46-1, its application will become more common.

Reference:
Article; Kinoshita, Hidenori; Fukumoto, Hiroki; Ueda, Akihiro; Miura, Katsukiyo; Tetrahedron; vol. 74; 14; (2018); p. 1632 – 1645;,
Bromide – Wikipedia,
bromide – Wiktionary

Some common heterocyclic compound, 4549-33-1, name is 1,9-Dibromononane, molecular formula is C9H18Br2, 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. 4549-33-1

n-BuLi (1.63 M in hexane, 4.0 mL, 6.52 mmol) was added to a solution of iPr2NH (0.62 mL, 4.4 mmol) in tetrahydrofuran (THF) (5 mL) at 0C, and the whole mixture was stirred for 30 min at 0C. 3-Picoline (0.39 mL, 4.02 mmol) was added to the mixture at -78C, and the whole mixture was stirred for 20 min. Then, 1,9-dibromononane (2.43 mL, 12 mmol) was added to the mixture, and the whole mixture was gradually warmed to r.t. with stirring overnight. Sat. NaHCO3aq. was added to the reaction mixture, and the whole mixture was extracted with AcOEt. The combined organic layer was washed with brine and dried (Na2SO4). Removal of the solvent under reduced pressure to give a crude product, which was purified by SiO2 column chromatography (hexane-AcOEt=8 : 1) to give 5b(388 mg, 33%).1H-NMR (500 MHz, CDCl3) delta: 8.35-8.30 (2H, m), 7.39 (1H, d, J=7.7 Hz), 7.10 (1H, dd, J=7.7, 4.9 Hz), 3.30 (2H, t, J=6.9 Hz), 2.50 (2H, t, J=7.7 Hz), 1.74 (1H, quint, J=7.1 Hz), 1.53-1.48 (2H, m), 1.35-1.12 (12H, m). 13C-NMR (125 MHz, CDCl3) delta: 149.6, 146.8, 137.6, 135.5, 123.0, 33.8, 32.7, 32.5, 30.8, 29.11, 29.10, 29.07, 28.8, 28.4, 27.9. IR (KBr) cm-1: 2926, 2854, 1574, 1422, 1026. ESI-TOF-MS m/z: 298 (M+H)+. HRESI-TOF-MS m/z: 298.1163 (Calcd for C15H25NBr: 298.1170).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 4549-33-1, its application will become more common.

Reference:
Article; Arai, Masayoshi; Kamiya, Kentaro; Shin, Dayoung; Matsumoto, Hirokazu; Hisa, Tomoya; Setiawan, Andi; Kotoku, Naoyuki; Kobayashi, Motomasa; Chemical and Pharmaceutical Bulletin; vol. 64; 7; (2016); p. 766 – 771;,
Bromide – Wikipedia,
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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, 327-52-6

Example 1: Preparation of (S)-1-chloro-3-(2,4,5-trifluorophenyl)propan-2-ol (formula 4) [Show Image] Preparation of 2,4,5-trifluorophenylmagnesium chloride solution: 700 mL of tetrahydrofuran was charged into reactor and cooled to 0 C, followed by the consecutive addition of 350 mL 2 M i-propylmagnesium chloride and 69 mL 1-bromo-2,4,5-trifluorobenzene applying stirring and maintaining temperature of the reaction mixture between 0 C and 5 C. After the addition, the reaction mixture was stirred gently for 1 h at 0 C to 5 C and for 3 h at 22 C obtaining the solution of 2,4,5-trifluorophenylmagnesium chloride.Determination of activity of the obtained solution: 0.25 g of iodine was weighed into small reaction flask and titrated with the solution obtained. When darkly brown solution turned its color to white suspension, the consumption of solution was ready. Typical consumption was about 1.85 mL/mmol of iodine.Conversion to compound of formula 4: To the whole amount of above prepared solution of Grignard reagent 28 mL of (S)-epichlorohidrin (formula 3) was added during stirring, followed by the addition of 0.80 g copper(I) chloride. Exotermic reaction started and when inner temperature raised to 40 C, external cooling was applied, lowering the internal temperature to 25 C. 28 mL of (S)-epichlorohidrin divided into two equal portions were added. After the addition, the reaction mixture was stirred for 5 h at 25 C, followed by the addition of 75 mL acetic acid and 750 mL methyl tert-butyl ether. The resulted mixture was washed consecutively with 700 mL water; mixture of 700 mL water, 80 mL brine, 80 mL 20% ammonium chloride, and 750 mL 2% sodium bicarbonate. Organic phase was evaporated at 60 C and 5 mbar, to yield 131 g of crude product of compound of formula 4 in the form of yellowish oil. 1H NMR (DMSO-d6): delta 2.64 (dd, 1H), 2.83 (dd, 1H), 3.49-3.64 (m, 2H), 3.85 3.90 (m,1H), 5.31 (d,1H), 7.37-7.48 (m, 2H).

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; LEK Pharmaceuticals d.d.; EP2397141; (2011); A1;,
Bromide – Wikipedia,
bromide – Wiktionary