Month: February 2021

Reference of 6911-87-1, 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. 6911-87-1 name is 4-Bromo-N-methylaniline, 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.

37.0 mg (0.2 mmol) of N-methyl-4-bromoaniline, 81.2 mg of ethyl bromodifluoroacetate (0.4 mmol), 2.5 mg (0.02 mmol) of cuprous acetate, 19.1 mg (0.04 mmol) of X-phos, 32.7 mg (0.2 mmol) of cesium carbonate were added to 2 mL of DMF solvent. The reaction was carried out at 110 C for 12 hours, after the reaction was completed, it was cooled, filtered, and the filtrate was evaporated. The solvent was removed and the residue was chromatographed on silica gel. It was washed with a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 8:1. The effluent was collected according to the actual gradient, detected by TLC, and the effluent containing the product was combined. The solvent was distilled off by a rotary evaporator. Drying in vacuo to give the yellow liquid -N-(4-bromophenyl)-N-methylformamide 26.0 mg, yield 61%.

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

Reference:
Patent; Wenzhou University; Zhang Xiaohong; Li Xiaofang; Zhang Xingguo; (15 pag.)CN108774147; (2018); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 766-46-1, The chemical industry reduces the impact on the environment during synthesis 766-46-1, name is 2′-Bromophenylacetylene, I believe this compound will play a more active role in future production and life.

General procedure: To a solution of sulfonyl azides 1 (0.6 mmol), o-bromo-phenylacetylenes 2 (0.5 mmol), aromatic amines 3 (0.55 mmol), and CuI (0.05 mmol) in DMSO (2 mL) in Schlenk tube was added TEA (0.5 mmol) slowly via a syringe. The reaction solution was stirred at room temperature under N2 for 2 h. The solution was then added to CuI (0.05 mmol), K2CO3 (1 mmol), and l-proline (0.2 mmol), and the mixture was stirred at 60 C under N2 for 4 h. The reaction mixture was partitioned between ethyl acetate and saturated aq NH4Cl, the organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by column chromatography on silica gel with petroleum ether and ethyl acetate (6:1 to 9:1).

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, 2′-Bromophenylacetylene, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Jin, Hongwei; Zhou, Bingwei; Wu, Zhi; Shen, Yang; Wang, Yanguang; Tetrahedron; vol. 67; 6; (2011); p. 1178 – 1182;,
Bromide – Wikipedia,
bromide – Wiktionary

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. 1073-06-9, name is 1-Bromo-3-fluorobenzene belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. SDS of cas: 1073-06-9

General procedure: A mixture of a fluorinated aryl halide (2.0 mmol), a carbazole (0.5 mmol), and a base (2.0 mmol) in solvent (2 mL) was allowed to react under air atmosphere. The reaction mixture was heated to the specified temperature for 24 h. After reaction completion, the mixture was added to brine (15 mL) and extracted with CH2Cl2 (3 ¡Á 15 mL). The combined extract was concentrated under reduced pressure and the product was isolated by short chromatography on a silica gel (200-300 mesh) column.

The synthetic route of 1073-06-9 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Wang, Lei; Ji, Enhui; Liu, Ning; Dai, Bin; Synthesis; vol. 48; 5; (2016); p. 737 – 750;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 4333-56-6, These common heterocyclic compound, 4333-56-6, name is Bromocyclopropane, 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 stirred suspension of magnesium turnings (300 mg, 12.3 mmol) in THF (2.0 mL) was added commercially available cyclopropyl bromide (0.800 mL, 9.99 mmol) in THF (17.2 mL) dropwise at room temperature over 30 min. During this operation, the reaction continued refluxing without heating. After the addition of the halide was completed, the mixture was stirred at room temperature for 5 h. The concentration of this solution of 40 was determined by titration as shown below. Titration. After an exactly 0.150-mL aliquot of the Grignard solution of 40 was quenched with an exactly known volume (0.250 mL) of a 1.000 M HCl standard solution (purchased from Yoneyama Yakuhin Kogyo, Co., Ltd. (Japan)), the mixture was then titrated with a 0.500 M NaOH standard solution (purchased from Yoneyama Yakuhin Kogyo, Co., Ltd. (Japan)) (0.352 mL) with methyl orange as an indicator to determine its concentration to be 0.49 M. Thus, the yield of the Grignard reagent was 98% based on the halide. In several runs, the Grignard concentrations usually fell within a range between 0.48 and 0.51 M.

Statistics shows that Bromocyclopropane is playing an increasingly important role. we look forward to future research findings about 4333-56-6.

Reference:
Article; Sugano, Goshi; Kawada, Kojiro; Shigeta, Masayuki; Hata, Takeshi; Urabe, Hirokazu; Tetrahedron Letters; vol. 60; 13; (2019); p. 885 – 890;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 1647-23-0,Some common heterocyclic compound, 1647-23-0, name is 1-Bromo-3,3-dimethylbutane, molecular formula is C6H13Br, 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.

Into a 1 L round bottom flask equipped with a dropping funnel and a reflux condenser, 14.1 g (580 mmol) of shaved magnesium was added and 60 ml THF was added. Magnesium was etched slightly with a few iodine crystals, then 2 g of 1-bromo-3,3-dimethyl-butane was added and the mixture was locally heated. After the onset of Grignard formation, the remainder of 1-bromo-3,3-dimethyl-butane (total 88.1 g, 553 mmol) in 350 ml of THF was added within 20 minutes. The mixture was refluxed for 1.5 hours and then cooled to room temperature. In a separate 2 L round bottom flask, 63.9 g (464 mmol) of 2-chloro-benzonitrile and 141 mg (0.16 mol%) of copper (I) iodide were dissolved in 265 ml of THF. The Grignard solution was added dropwise over 30 minutes and the reaction mixture was refluxed for 3 hours. After standing overnight at room temperature, a mixture of 190 ml of water and 127 ml of concentrated hydrochloric acid was added very carefully to produce a strongly exothermic reaction. The mixture was stirred at 50 C. for 1 hour and the layers were separated. The aqueous layer was extracted twice with 150 ml each of toluene. The combined organic layers were washed twice with 2 M sulfuric acid, once with saturated sodium bicarbonate solution and once with saturated sodium chloride solution. After drying over magnesium sulfate, the solvent was evaporated in vacuo to give 103.8 g (quantitative) of the desired phenone as a slightly brown oil.

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-3,3-dimethylbutane, its application will become more common.

Reference:
Patent; LUMMUS NOVOLEN TECHNOLOGY GMBH; (91 pag.)JP6196581; (2017); B2;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 65185-58-2, These common heterocyclic compound, 65185-58-2, name is 2-Bromophenethylamine, 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 95 (4R,6R,7R)-1-(2-(2-bromo)phenyl)ethyl-4,7-di(tert-butyldimethyl-silyloxy)-4,5,6,7-tetrahydro-1H-indole-4,6-carbolacame (22). A solution of allylketone III-1 (example 2) (500 mg, 1.14 mmol) in dicloromethane (50 mL) was placed into a gas-washing bottle and cooled down to -78 C. in a dry ice bath. The mixture was then flushed with argon for 5 min, oxygen for 5 min and then with an oxygen/ozone mixture for 12 min The end of the reaction was indicated by a 5% potassium iodide/water solution turning orange, which was located at the exit. Afterwards, the reaction mixture was flushed for 10 min with argon to remove excess ozone. The gas-washing bottle was taken from the cooling bath and the content was slowly warming up to room temperature. The solvent was evaporated under reduced pressure to afford an oil (500 mg) which was dissolved in a 1:1 mixture of dichloromethane-acetic acid (2 mL). The resultant solution was treated at 0 C. with 2-(2-bromo)phenylethylamine (0.18 mL, 1.25 mmol) and it was stirred for 30 min The reaction mixture was neutralized with powdered sodium bicarbonate and it was diluted with dichloromethane and water. The organic layer was separated and the aqueous layer was extracted twice with dichloromethane. All the combined organic extracts were dried (anh. Na2SO4), filtered and concentrated under reduced pressure. The obtained residue was purified by columm chromatography over silica gel, previously neutralized with triethylamine-hexanes (5:95), using diethyl ether-hexanes (5:95) as cluent to afford compound 22 (150 mg, 23%) as a colourless oil. [alpha]D20=-109.0 (c1.3, in CHCl3). 1H NMR (250 MHz, CDCl3) delta 7.60-7.50 (m, 1H, ArH), 7.15-7.07 (m, 2H, 2*ArH), 6.60-6.55 (m, 1H, ArH), 6.50 (d, J=2.7 Hz, 1H, H-2), 6.14 (d, J=2.7 Hz, 1H, H-3), 4.50 (dd, J=5.5 and 3.5 Hz, 1H, H-6), 4.18 (d, J=3.5 Hz, 1H, H-7), 4.07 (m, 2H, NCH2), 3.29-3.19 (m, 1H, CHHAr), 3.09-2.93 (m, 1H, CHHAr), 2.47 (d, J=10.5 Hz, H-5eq), 2.38 (dd, J=10.5 and 5.5 Hz, H-5ax), 0.97 (s, 9H, C(CH3)3), 0.88 (s, 9H, C(CH3), 0.22 (s, 3H, CH3), 0.18 (s, 3H, CH3), 0.14 (s, 3H, CH3) and 0.14 (s, 3H, CH3) ppm. 13C NMR (63 MHz, CDCl3) delta 175.9 (C), 137.2 (C), 132.6 (CH), 130.8 (CH), 128.7 (CH), 127.9 (CH), 124.7 (C), 123.8 (C), 123.4 (C), 121.2 (CH), 103.5 (CH), 76.5 (CH), 74.2 (C), 64.1 (CH), 46.5 (CH2), 38.3 (CH2), 38.2 (CH2), 25.7 (2*C(CH3)3), 18.2 (C(CH3)3), 18.0 (C(CH3)3), -2.9 (CH3), -3.0 (CH3), -4.1 (CH3) and -4.3 (CH3) ppm. IR (KBr) 1799 (C=O) cm-1. MS (CI) m/z (%) 606 and 608 (MH-). HRMS calcd for C29H45O4NSi281Br (MH+): 608.2050; found, 608.2043.

Statistics shows that 2-Bromophenethylamine is playing an increasingly important role. we look forward to future research findings about 65185-58-2.

Reference:
Patent; UNIVERSIDADE DE SANTIAGO DE COMPOSTELA; US2011/313032; (2011); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Related Products of 52548-00-2, 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 52548-00-2 as follows.

PREPARATIVE EXAMPLE 44; .Ph In aBH4; Step i; A mixture of 3-bromo-6-fluoro-o-xyle?e (25.37g, 432 mmol) in anhydrous CCI4 (250 mL) was treated with NBS (44.5g, 864 mmol) and benzoyl peroxide (310 mg) and then heated at reflux overnight. The mixture was cooled to 0 C and filtered, washing with hexanes. The filtrate was concentrated and chromatographed (hexanes) to give 44A as an colorless oil (41.57g, with minor mono-bromo impurities).

According to the analysis of related databases, 52548-00-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; SCHERING CORPORATION; MCCORMICK, Kevin D.; DONG, Li; BOYCE, Christopher W; DE LERA RUIZ, Manuel; ZHENG, Junying; WON, Walter S.; WO2010/42475; (2010); 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 766-81-4 as follows. SDS of cas: 766-81-4

EXAMPLE 26; Preparation of 2-Amino-5-(5-chloro-2-methylthien-3-yl)-3-methyl-5-(3-pyrimidin-5-ylphenyl)-3,5-dihydro-4H-imidazol-4-one; Step a); Preparation of Compound 14; A mixture of 13 (3.17 g, 12.3 mmol), 3-bromophenylacetylene (2.44 g, 13.5 mmol; see MEC00775; dated Aug. 15, 2003), bis(triphenylphosphine)palladium(II) chloride (0.258 g, 0.360 mmol), copper(I) iodide (0.046 g, 0.240 mmol) and triethylamine (3.70 g, 36.8 mmol) in dimethylformamide (60 mL) was stirred at room temperature for 1.5 h. The mixture was diluted with ethyl acetate (300 mL), washed with water (2¡Á100 mL), brine (3¡Á100 mL), dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography (silica, hexanes) to afford 14 as a yellow oil, which was a mixture of product and an unidentified by-product (which was removed during purification in the following step): APCI MS m/z 311 [C13H8BrClS+H]+.

According to the analysis of related databases, 766-81-4, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Wyeth; US2007/4786; (2007); 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. 156682-52-9, name is 1,4-Dibromo-2,3-difluorobenzene, This compound has unique chemical properties. The synthetic route is as follows., name: 1,4-Dibromo-2,3-difluorobenzene

Under a nitrogen atmosphere, 7.08 g (35.9 mmol) of 3-bromo-2-chlorothiophene (Tokyo Chemical Industry Co., Ltd.) and 70 ml of THF (dehydrated grade) were added to a 300 ml Schlenk reaction vessel. The solution was cooled to 0 C., and 18.5 ml (37.0 mmol) of a THF solution of isopropylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0 C. for 1 hour (preparation of Grignard reagent). Meanwhile, in a nitrogen atmosphere, 5.90 g (43.2 mmol) of zinc chloride (Wako Pure Chemical Industries, Ltd.) and 60 ml of THF (dehydration grade) were added to another 500 ml Schlenk reaction vessel and cooled to 0 C. To the obtained white fine slurry solution, the Grignard reagent of 3-bromo-2-chlorothiophene previously prepared was dropped using Teflon cannula, and further 5 ml of THF (dehydration grade) was charged into a 300 ml Schlenk reaction vessel And Teflon cannula were added while washing. The resulting mixture was stirred at 0 C. for 30 minutes and further at room temperature for 90 minutes. 3.26 g (12.0 mmol) of 1,4-dibromo-2,3-difluorobenzene (Tokyo Chemical Industry Co., Ltd.) as a white fine slurry solution of the produced 2-chlorothienyl-3-zinc derivative and tetrakis Phosphine) palladium (Tokyo Chemical Industry Co., Ltd.) (0.181 mmol, 1.51 mol% based on 1,4-dibromo-2,3-difluorobenzene) was added. After conducting the reaction at 45 C. for 4 hours, the reaction vessel was cooled with water and the reaction was stopped by adding 150 ml of 1N hydrochloric acid. The mixture was extracted with toluene, and the organic phase was washed with brine and dried over anhydrous sodium sulfate. The residue was purified by silica gel column chromatography (developing solvent: toluene / hexane = 1: 1). The mixture was concentrated under reduced pressure, and the obtained residue was washed with 20 ml of hexane. The obtained residue was purified by recrystallization from heptane / toluene = 2/1 to obtain 1.88 g of 1,4-di (2-chlorothienyl-3 -) – 2,3-difluorobenzene as a colorless solid(Yield 45%).

According to the analysis of related databases, 156682-52-9, the application of this compound in the production field has become more and more popular.

Reference:
Patent; TOSOH CORPORATION; MIYASHITA, MASATO; WATANABE, MAKOTO; HACHIYA, HITOSHI; TANABIKI, MASAO; (26 pag.)JP2017/226629; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Application 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.

General procedure: A mixture of CuI (190mg, 1mmol), 4-methyl-1H-imidazole (1.64g, 20mmol), Cs2CO3(3.25g, 10mmol), 3-bromo-5-(trifluoromethyl)aniline (2.40g, 10 mmol), 1-(5,6,7,8-tetrahydroquinolin-8-yl)ethanone (350mg, 2mmol) and DMF (30mL) was added to a bottom, the bottom was evacuated and backfilled with argon (this procedure was repeated three times), then the mixture was heated to 130 C for 24 h under argon. After cooling to room temperature, the solvent was removed under vacuum and the residue was purified by column chromatography on silica gel to afford the crude product. The crude product was recrystallized as a white solid (1.7 g, 71%)

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 3-Bromo-5-(trifluoromethyl)aniline, its application will become more common.

Reference:
Article; Wang, Deping; Zhang, Zhang; Lu, Xiaoyun; Feng, Yubing; Luo, Kun; Gan, Jirong; Yingxue, Liu; Wan, Junting; Li, Xiang; Zhang, Fengxiang; Tu, Zhengchao; Cai, Qian; Ren, Xiaomei; Ding, Ke; Bioorganic and Medicinal Chemistry Letters; vol. 21; 7; (2011); p. 1965 – 1968;,
Bromide – Wikipedia,
bromide – Wiktionary