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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1003-99-2, 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. 1003-99-2, name is 2-Bromo-5-fluoroaniline, This compound has unique chemical properties. The synthetic route is as follows.

To a 2-L reactor equipped with a mechanic agitator, a condenser, a thermocouple, a baffle, and nitrogen inlet were charged 228 g of water, 200 g of 2-bromo-5-fluoroaniline and 80 g of 4-nitrophenol. To this mixture was charged 96percent sulfuric acid in 10-30 min at 20-120¡ã C. The mixture was heated to 135-140¡ã C. and 194 g of glycerol was charged into the reactor over two hours at 135-145¡ã C. The mixture was held at 135-145¡ã C. for 1 hour after the addition. The reaction mixture was cooled to below 20-50¡ã C. and slowly transferred to a 5-L reactor containing 1100 g of water and 1210 g of toluene. The 2-L reactor was washed with 300 g of water and the wash was combined into the 5-L reactor. The pH of the contents in the 5-L reactor was adjusted to pH 8-10 by adding approximately 1233 g (1370 mL) ammonium hydroxide (28-30percent NH3) at 20-40¡ã C. The mixture was stirred at room temperature for 15 min and the solid by-product was filtered off while the filtrate was retained. The filter cake was washed with 400 ml of toluene and the all the filtrate was combined and charged a 3-L reactor. About 500 ml of 8.5percent KOH solution was charged into the 3-L reactor and stirred for 10 min and bottom aqueous layer was spit off. A second portion of 500 ml of 8.5percent KOH solution was added and the mixture was stirred for 15 min and the bottom aqueous layer was split off. Water 500 ml was added and stirred for 15 min before the bottom aqueous layer was split off. The organic layer was heated to distill off about 100-200 ml of toluene to azeotropically remove water. A clear solution will be obtained. Typical yield 178 g real 8-bromo-5-fluoroquinoline, 75percent.Alternatively, 8-bromo-5-fluoroquinoline was prepared by adding a warm mixture containing 2-bromo-5-fluoroaniline (100 g, 1.0 eq), 4-nitrophenol (40 g, 0.54 eq), and glycerol (97 g, 2.0 eq) over 1.5 hours to sulfuric acid (267 ml) and water (114 mL) at 140-150¡ã C. The initial mixture showed 37.8percent 4-nitrophenol by relative HPLC area percent. Samples showed 4.7percent 4-nitrophenol immediately after adding 50percent of mixed starting materials and 5.0percent immediately after adding all of the materials. The yield upon workup was 87.5percent, with total impurities 0.29percent. Addition of less (0.46 eq, 34 g) 4-nitrophenol also successfully produced the intermediate of interest at acceptable yield.

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; Wyeth; US2007/27160; (2007); A1;,
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65896-11-9, 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 65896-11-9 as follows.

To a suspension of sodium perborate tetrahydrate (135.374 g., 886.4 mmol) in 500 mL acetic acid at 55 C. was added dropwise a solution of 2-bromo-6-fluoro-phenylamine (33.685 g., 177.271 mmol) in 70 mL acetic acid over 1 hour. The reaction mixture was stirred at 55 C. for an additional 3 hours, then cooled to 0 C. in an ice bath. Insoluble materials were removed by filtration through a plug of celite, which was rinsed with 100 mL acetic acid. The combined acetic acid fractions were added to 3 L ice water with stirring to give a waxy solid which was removed by filtration. The crude solid was dissolved in 250 mL ethyl acetate, washed three times with 200 mL of 10% aqueous hydrogen chloride, 200 mL saturated sodium bicarbonate and 100 mL brine. The solution was concentrated in vacuo to give 11.51 g of 1-bromo-3-fluoro-2-nitro-benzene as a red oil, 1H NMR (CDCl3, 300 MHz) delta: 7.26 (m, 1H), 7.38 (m, 1H), 7.49 (m, 1H)

According to the analysis of related databases, 65896-11-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Roche Palo Alto LLC; US2007/15744; (2007); A1;,
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In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 10016-52-1, name is 2,8-Dibromodibenzo[b,d]furan belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 10016-52-1

Dibromodibenzo [b, d] furan (1.0 g, 3.07 mmol, 1.0 eq) was dissolved in tetrahydrofuran (35 ml) followed by the addition of Tetrahydrofuran To a 25 ml flaskThe mixture was gradually added at 45 and stirred. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove the solvent. The solvent was distilled off (100 ml X 3), and the filtrate was dried over MgSO 4, filtered, and dried to obtain dibenzo [b, d] furan-2,8-diylbis ) Phenyl) methanol (1.7 g). The solution was dissolved in 35 ml of methanol and 35 ml of hydrogen chloride, followed by heating and stirring at 80 C for 2 hours. After the reaction was completed, the solvent was distilled off to remove the solvent, and then a small amount of distilled water was added thereto. After the work-up, water was removed with MgSO 4 and filtered to obtain G-4 (1.3 g, yield 63.17%

The synthetic route of 10016-52-1 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Korea Jiao Tong University Academic Cooperation; Lee, Ji Hun; Choe, Sung Hyun; Yun, Poo Yong; Yun, Moo Sang; (25 pag.)KR101638767; (2016); B1;,
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452-92-6, Name is 5-Bromo-2,4-difluoroaniline, 452-92-6, 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.

A solution of 2,4-difluoro-6-bromoaniline (5 g, 24 mmol), salicylaldehyde (2.5 mL, 24 mmol) and p-toluenesulfonic acid (14 mg, 0.07 mmol) in toluene (120 mL) was heated to reflux in a Dean-Stark apparatus for 2.5 h and then allowed to cool to ambient temperature. After adding triethylamine (1 mL) the reaction mixture was concentrated to give the crude title compound (7.3 g, 97%) which was used without further purification. 1H-NMR (400 MHz, CDCl3) 6.95-6.99 (m, 1H), 7.01-7.06 (m, 2H), 7.39-7.45 (m, 2H), 7.48-7.52 (m, 1H), 8.66 (s, 1H), 12.69 (s, 1H). (m/z)=312+314 (M+H)+.

Statistics shows that 5-Bromo-2,4-difluoroaniline is playing an increasingly important role. we look forward to future research findings about 452-92-6.

Reference:
Patent; N.V. Organon; US2008/90804; (2008); A1;,
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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. 626-40-4, name is 3,5-Dibromoaniline, This compound has unique chemical properties. The synthetic route is as follows., 626-40-4

(1) Preparation of diazonium salt: 100 1 ^ beaker by adding 5.011483, 5 dibromoaniline and 8 1 ^ 20% hydrochloric acid, 0 ~ 5 C slowly to the suspension by adding 1.5232 g of aqueous solution of sodium nitrite , The suspension becomes clear after adding urea to remove excess nitrous acid, sodium acetate solid to adjust the pH to 5, the clarified liquid set in ice water in reserve.(2) Preparation of o-methoxyanilide methanesulfonate:50 mL round bottom flask was added 10 mL of water and 2.3553 g sodium bisulfite, sodium bisulfite was dissolved and added 0.7221G paraformaldehyde, 60 C reaction 35 min after the drop of 2.4610 g o-methoxy aniline, after 2 h reaction to stop heating, o-methoxy anilino-methyl methanesulfonate mixture.(3) Preparation of azobenzene compound:After the mixture obtained in step (2) was cooled to room temperature, the mixture was slowly added dropwise to the diazonium salt obtained in the step (1), At this time, to clarify the diazonium salt solution gradually dark red viscous liquid, temperature control at 0 ~ 5 C reaction 6 h after the end of the reaction. Add 50 mL of 30% sodium hydroxide aqueous solution, dark red viscous liquid into yellow turbid liquid, nitrogen protection under 50 C hydrolysis 7 h, after the end of the reaction with hydrochloric acid to adjust the pH value of about 8, the crude product by thin layer chromatography , The dye: 0,5 & dibromo-3-methoxy-4-amino azobenzene 2.237g (yield 29%).

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; Lingnan Normal University; Song Xiumei; Feng Zongcai; (13 pag.)CN105001664; (2017); B;,
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In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 955959-84-9, name is 4-(4-Bromophenyl)dibenzo[b,d]furan belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. 955959-84-9

In the argon atmosphere, weighing intermediate respectively (1-1) 3.2g (10.0mmol), intermediate (A-2-1) 5.8g (10.0mmol), Pd2(dba)30.14g (0.15mmol), P (tBu)3HBF40.087g (0.3mmol), tertiary butyl alcohol sodium 1.9g (20.0mmol), adding anhydrous xylene 50 ml, heating reflux for 8 hours.After the reaction, the reaction mixture is cooled to 50 ¡ãC, filtered through diatomaceous earth/silica gel, concentrated filtrate. The obtained concentrated residue after being refined with silica gel column chromatography, using toluene recrystallization, get 2.9g of the white crystal (yield 35percent).

The synthetic route of 955959-84-9 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Idemitsu Kosan Co., Ltd.; Jiateng, Pengxi; Sounei, Shenhao; Zhou, Qiaozhenghe; Tengshan, Gaoguang; (107 pag.)CN105431417; (2016); A;,
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586-61-8, 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. 586-61-8 name is 1-Bromo-4-isopropylbenzene, 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.

General procedure: n-BuLi (1.55 M solution in hexane, 2.32 mL, 3.6 mmol) was added dropwise to a solution of 4-methylphenyl bromide (513 mg, 3.0 mmol) in THF (6.0 mL) at -50 C under Ar atmosphere. After 30 min, DMF (278 muL, 3.6 mmol) was added and the obtained mixture was gradually warmed to r.t. After 1 h at the same temperature, NH2OHxHCl (313 mg, 4.5 mmol) and K2CO3 (622 mg, 4.5 mmol) were added and the obtained mixture was stirred for 2 h at r.t. Then, after removal of the solvent under reduced pressure, toluene (3.0 mL), DPPA (1.61 mL, 7.5 mmol), and DBU (1.57 mL, 10.5 mmol) were added to the obtained residue under Ar atmosphere. After being stirred for 16 h under refluxing conditions, the mixture was cooled to r.t. and then, saturated NaHCO3 aq. (15.0 mL) was added. After being stirred for 5 min, the mixture was diluted with water (5.0 mL). The aqueous layer was then washed with AcOEt (25.0 mL) and acidified with 1.0 M HCl aq. to pH 2. The aqueous layer was extracted with AcOEt (2 x 25.0 mL). Removal of the solvent, followed by purification of the residue by short column chromatography on neutral silica gel (AcOEt: hexane = 1:3-1:1) gave 5-(4?-methylphenyl)tetrazole 3A (336.1 mg, 70%).

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

Reference:
Article; Kobayashi, Eiji; Togo, Hideo; Tetrahedron; vol. 74; 31; (2018); p. 4226 – 4235;,
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Some common heterocyclic compound, 1575-37-7, name is 4-Bromobenzene-1,2-diamine, molecular formula is C6H7BrN2, 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. 1575-37-7

General procedure: A solution of 10 mmol of the appropriate benzene-1,2-diamine in3.5 mL of acetic acid (AcOH) and 1 mL of water was cooled to 0-5 C,followed by the addition of 15 mmol of sodium nitrite in 2 mL ofwater. The mixture was stirred for 2 h at room temperature. Afterthe completion of the reaction, a solventwas evaporated and the residuewasco-evaporatedwith toluene (3 ¡Á 20mL). The crude productwas partitioned between water (20 mL) and ethyl acetate (20 mL),the organic phase was washed with the saturated solution of sodiumhydrogen carbonate and dried overmagnesiumsulfate (MgSO4). Theproducts were purified by crystallization from nitromethane and/orby column chromatography on silica gel using a chloroform – methanol97:3-95:5 v/v mixture as eluent. Reaction products were analyzedby use of mass-spectrometry (Waters Q-TOF Premier MassSpectrometer) and NMR spectroscopy (Varian INOVA 500 Spectrometer,see Supp. Fig. 1). Purity of the products was assessed using internalstandard quantitative NMR method (qNMR) [49]. It shouldbe noted that the formal qNMR-derived purity determined for 4-BrBt, 4-ClBt, 5,6-Cl2Bt and 5,6-Br2Bt increased significantly upon additiona small amount of water to the DMSO solution, which increasedproton exchange rates. This observation indicates that thenuclear relaxation process accompanying protomeric equilibrium(generally N1-H and N3-H forms predominates) significantly contributeto the obtained NMR spectra, the best proof of which is thestrong broadening of the H-7 resonance line in 4-BrBt and 4-ClBt(Supp. Fig. 1A,B).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1575-37-7, its application will become more common.

Reference:
Article; Szymaniec-Rutkowska, Anna; Bugajska, Ewa; Kasperowicz, S?awomir; Mieczkowska, Kinga; Maciejewska, Agnieszka M.; Pozna?ski, Jaros?aw; Journal of Molecular Liquids; vol. 293; (2019);,
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A common compound: 111721-75-6, name is 2-Bromo-3-fluoroaniline, 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. 111721-75-6

To a stirred solution of compound Xlla (155 g, 1.15 mmol) in dichloromethane (2 L) at 0 C under nitrogen atmosphere were added pyridine (750 mL, 5 vol) and 2-bromo-3-fluroaniline (218.0 g, 1.15 mmol). The resulting mixture was continued to stir at room temperature for 16 hours. After that the reaction mixture was quenched with water extracted with dichloromethane (2 x 5 L). The combined organic phase was washed with 1.5N HCl solution (2 x 3 L), brine (1 x 2 L), dried over Na2S04 and concentrated in vacuo. The obtained crude product was purified by column chromatography using silica gel (60-120 mesh) eluting with 20% of ethyl acetate in petroleum ether to get compound Xllb. Yield: 240 g, 64.67% (over a two steps); LC-MS Calc. for CnHnBrFN02, 288.12; Obs: 290.0 [M++2H]; NMR (300 MHz, DMSO-d6): delta 9.26 (s, 1H), 7.61-7.59 (d, 1H, J=8.19 Hz), 7.54-7.49 (m,lH), 7.41-7.34 (m, 1H), 7.17- 7.11 (m, 1H), 5.79-5.75 (d, 1H, J=12.33 Hz), 3.97-3.95 (m, 2H), 1.30-1.25 (m, 3H).

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, 111721-75-6, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BUGWORKS RESEARCH INDIA PVT LTD; PEER MOHAMED, Shahul Hameed; BHARATHAM, Nagakumar; KATAGIHALLIMATH, Nainesh; SHARMA, Sreevalli; NANDISHAIAH, Radha; RAMACHANDRAN, Vasanthi; VENKATARAMAN, Balasubramanian; (221 pag.)WO2018/225097; (2018); A1;,
Bromide – Wikipedia,
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