Month: July 2021

Electric Literature of 1137142-58-5, 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. 1137142-58-5 name is 2-Bromoimidazo[2,1-b][1,3,4]thiadiazole, 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.

Intermediate 23; lmidazo[2,1-b][1,3,4]thiadiazol-2-yl-(4-methoxyphenyl)amine; A mixture of 2-bromo-imidazo[2,1-b][1 ,3,4]thiadiazole (1.0 g, 4.90 mmol) and p- anisidine (19.6 mmol, 2.41 g) in trifluoroethanol (12 mL) was heated under microwave irradiation at 170C for 1 hour. On cooling, the mixture was diluted with dichloromethane (10 mL) and purified by column chromatography (Biotage/Flash, silica, methanol:dichloromethane 0.2:9.8 to 1 :9). The residue obtained was triturated with diethylether and few drops of methanol to give imidazo[2,1-b][1 ,3,4]thiadiazol-2-yl-(4-methoxyphenyl)amine as a white solid (355 mg, 29% yield). 1H-NMR (300 MHz, CDCI3): delta 8.01 (s, 1 H), 7.55 (s, 1 H), 7.44 (d, J = 8.9, 2H), 7.22 (s, 1H), 6.90 (d, J = 8.8, 2H), 3.80 (s, 3H). MS (ES+) m/z 247 (M+H)+ (MW: 246.29).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 2-Bromoimidazo[2,1-b][1,3,4]thiadiazole, and friends who are interested can also refer to it.

Reference:
Patent; CENTRO NACIONAL DE INVESTIGACIONES ONCOLOGICAS (CNIO); WO2009/40552; (2009); A2;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 5003-71-4, 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. 5003-71-4, name is 3-Bromopropan-1-amine hydrobromide, This compound has unique chemical properties. The synthetic route is as follows.

Triethylamine (30 mL) was added dropwise to 3-bromopropan-1-aminium bromide (10.84 g, 50 mmol) in DCM (50 mL). After 15 min stirring, di-tert-butyl dicarbonate (21.8 g, 100 mmol) in DCM (40 mL) was added dropwise to the solution for 1 h, and the resulting mixture was stirred for 2 days at room temperature. The resulting solution was washed with 1 N aqueous HCl, water × 2, saturated aqueous NaHCO3, and brine. The organic phase was dried with Na2SO4, and thes olvent was removed in vacuo to give tert-butyl (3-bromopropyl) carbamate (20.54 g, yield = 88%).

The chemical industry reduces the impact on the environment during synthesis 3-Bromopropan-1-amine hydrobromide. I believe this compound will play a more active role in future production and life.

Reference:
Article; Qin, Huihuan; Li, Lingling; Li, Kun; Xiaoqi, Yu; Chinese Chemical Letters; (2019); p. 71 – 74;,
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. 766-81-4, name is 3-Bromophenylacetylene, A new synthetic method of this compound is introduced below., HPLC of Formula: C8H5Br

Step b); Preparation of 1-(3-bromo-phenyl)-2-[5-propionyl-1-(2,2,2-trifluoro-ethyl)-1H-pyrrole-3-yl]-ethane-1,2-dione; A mixture of 1-[4-Iodo-1-(2,2,2-trifluoro-ethyl)-1H-pyrrole-2-yl)-propan-1-one (4.8 g, 0.145 mol), 1-bromo-3-ethynyl-benzene (2.62 g, 0.145 mol) CuI (137 mg, 0.725 mmol) and Pd(PPh3)4 (670 mg, 0.58 mmol) in a mixture of triethylamine (50 ml) and acetonitrile (20 ml) is heated to reflux for 2 hours before cooled down to room temperature. The volatile solvent is removed under reduced pressure, and the residue is partitioned between ethyl acetate (50 ml) and water (200 ml). The organic phase is dried with MgSO4 and is purified by flash chromatography with EtOAc/hexane (10/90-20/80) as eluent to afford the alkyne product as a yellow solid 4.6 g (82%). This solid stirred with KMnO4 (4.73 g, 2.5 mol), NaHCO3 (604 mg, 7.2 mmol) and MgSO4(2.16 g, 18 mmol) in a mixture of acetone (200 ml) and water (100 ml) at room temperature for two hours. The mixture is extracted with ether (2×50 ml) to afford the product as a yellow oil 4.5 g (90%). 1HNMR (DMSO-d6): delta (ppm) 1.03 (t, 3H), 2.92 (q, 2H), 5.38 (q, 2H) 7.56 (t, 1H), 7.74 (s, 1H), 7.92 (d, 1H), 7.95 (d, 2H), 8.06 (s, 1H), 8.12 (s, 1H).

The synthetic route of 766-81-4 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Wyeth; US2007/4786; (2007); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 2924-09-6, These common heterocyclic compound, 2924-09-6, name is 5-Bromo-2-fluoroaniline, 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.

A vial was charged with 5-bromo-2-fluoroaniline (1 g, 5.26 mmol), bis(pinacolato)diboron (1.6 g , 6.31 mmol), potassium acetate (1.03 g, 10.52 mmol), Pd(dppf)Cl2 · CH2C12 (129 mg, 0.158 mmol), and DMF (10 mL) under nitrogenatmosphere. After stirring for 2 h at 100 C the reaction mixture was concentrated in vacuo, the residue was triturated with EtOAc and filtered through a pad of celite. The filtrate was adsorbed on silica gel. Purification by flash silica gel chromatography using a gradient of 0- 30% EtOAc/hexane afforded 1.25 g of pinacol 3-amino-4-fluoroboronate as a light yellow oil (quant.): 1H NMR (CDC13, ppm) delta 1.36 (s, 12H), 3.71 (broad s, 2H), 7.00 (dd, 1H), 7.19 (m, 1H), 7.26 (dd, 1H); [M+H]+ m/z 238.

Statistics shows that 5-Bromo-2-fluoroaniline is playing an increasingly important role. we look forward to future research findings about 2924-09-6.

Reference:
Patent; SELEXAGEN THERAPEUTICS, INC.; VERNIER, Jean-michel; HOPKINS, Stephanie; BOUNAUD, Pierre-Yves; O’CONNOR, Patrick; MATTHEWS, David; BENDER, Steve; WO2012/125981; (2012); A2;,
Bromide – Wikipedia,
bromide – Wiktionary

Application of 3972-64-3, 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. 3972-64-3, name is 1-Bromo-3-(tert-butyl)benzene belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

A solution of bromo-tert- butylbenzene (4.62 g, 21.68 mmol) in THF (50 mL) was cooled to-78 °C then n- BuLi (2.5M, 9.1 mL) was added dropwise. The reaction was stirred for 30 min then a solution of 1-benzyl-piperidin-4-one (3.69 g, 19.5 mmol) in THF (10 mL) was added dropwise. After stirring for 30 min at-78 °C, the reaction was warmed to 0°C then quenched with water (50 mL). The reaction was diluted with ethyl acetate (100 mL); the organic was separated, washed with brine (50 mL), dried over magnesium sulfate and concentrated yielding an oil (6.94 g, 21.5 mmol), which was used in the next step without further purification; LC rt=2.98 min; MS (ESI) 306.2.

The synthetic route of 1-Bromo-3-(tert-butyl)benzene has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ELAN PHARMACEUTICALS, INC.; WO2005/87215; (2005); 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. 10269-01-9, name is (3-Bromophenyl)methanamine, A new synthetic method of this compound is introduced below., Product Details of 10269-01-9

Example 1. Synthesis of iV2-{[3′-(aminomethyl)biphenyl-3-yl]methyl}-iV4-{[mM5-4- (aminomethyl)cyclohexyl]methyl}-5-nitropyrimidine-2,4-diamine; To a mixture of 2,6-dichloro-5-nitropyrimidine (17.13 g, 88.30 mmol) and CH3CN (50 mL) at 0 0C was added a mixture of ^ra«5-(4-aminomcthyl-cyclohcxylmcthyl)-carbamic acid tert-butyl ester (21.40 g, 88.30 mmol) and lambdazetaN-diisopropylethylamine (15.4 mL, 88.30 mmol) in CH3CN (50 mL). The reaction mixture was allowed to warm to room temperature and stirred overnight. Volatiles were evaporated in vacuo and the residue purified by silica gel chromatography (Hexane/EtOAc 4:1) to afford tr°«5-4-[(2-chloro-5- nitro-pyrimidin-4-ylamino)-methyl]-cyclohexylmethyl}-carbamic acid tert-buty] ester (25.00 g, 71%) as an off-white solid.To a solution of 3-bromo-benzylamine (716 mg, 3.85 mmol) and. diisopropylethylamine (0.65 mL, 3.75 mmol) in dichloromethane (25 mL) was added /ralpha«lambda’-4-[(2-chloro-5-nitro- pyrimidin-4-ylamino)-methyl]-cyclohexylmethyl}-carbamic acid tert-butyl ester (1.01 g, 2.53 mmol). The rxn mixture was stirred at room temperature for 17 h, then partitioned between ethyl acetate and IM HCl solution. The organic phase was washed with satd NaHCtheta3 solution and brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel chromatography eluting with 0-3% MeOH in CH2Cl2 to afford 723 mg (52%) of (trans-4-{[2-(3-bromo-benzylamino)-5-nitro-pyrimidin-4- ylamino] -methyl) -cyclohexylmethyl)-carbamic acid tert-butyl ester as a pale yellow solid, m/z 549.3 (M + H)+.To a mixture of (fralphan>s-4-{[2-(3-bromo-benzylam.mo)-5-nitro-pyrimidin-4-ylamino]- methyl}-cyclohexylmethyl)-carbamic acid tert-butyl ester (50 mg, 0.091 mmol), (3- aminomethylphenyl)boronic acid HCl (26 mg, 0.137 mmol), tetrakis(triphenylphosphine)palladium (10 mg, 0.009 mmol), and sodium carbonate (38 mg, 0.360 mmol) was added dimethoxyethane (1.0 mL) and water (0.150 mL). The reaction mixture was sealed under N2 and heated at 90 0C for 5 h. The reaction mixture was partitioned between ethyl acetate (20 mL) and water (5 mL). The organic phase was washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by silica gel chromatography eluting with 0-80% 0.1 :1 :9 NH4OH/MeOH/CH2Cl2 in CH2Cl2 to furnish 21 mg (40%) of [?ralphar°-4-({2-[(3′-aminomethyl-biphenyl-3-ylmethyl)- amino]-5-nitro-pyrimidin-4-ylamino} -methyl)-cyclohexylmethyl]-carbamic acid tert-butyl ester as a yellow oil, m/z 576.4 (M + H) ‘ . ” A solution of [tralpha«lambda’-4-({2-[(3′-aminomethyl-biphenyl-3-yhnethyl)-amino]-5-nitro- pyrimidin-4-ylamino}-methyl)-cyclohexylmethyl]-carbamic acid tert-butyl ester (21 mg, 0.036 mmol) in dichloromethane (4.0 mL) was treated with 4 M HCl in dioxane (0.100 mL, 0.400 mmol). The reaction mixture was stirred at room temperature for 18 h and then concentrated. The crude product was purified silica gel chromatography eluting with 0- 100% 0.1:1:9 NH4OH/MeOH/CH2Cl2 in CH2Cl2 to give 16 mg (93%) of N2-{[3′-(aminomethyl)biphenyl-3-yl]methyl} -N4- {[trans-4-(aminomethyl)cyclohexyl]methyl} -5- nitropyrimidine-2,4-diamine, m/z 476.5 (M + H)+.

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; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; BOEHRINGER INGELHEIM PHARMA GMBH & CO. KG; WO2007/76247; (2007); 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 54962-75-3 as follows. Product Details of 54962-75-3

3-bromo-5-trifluoromethylaniline (720 mg, 5 mmol) was dissolved in concentrated hydrochloric acid, cooled to -10 C, and an aqueous solution of sodium nitrite (380 mg, 5.5 mmol) was added dropwise to react for 2 h. Cooled to -30 C, dropped into a concentrated hydrochloric acid solution of SnCl2 (3.40g, 15mmol) pre-cooled to -30 C, reacted at -20 C for 1h, warmed to room temperature, filtered, and dried to give 805 mg of a pale yellow solid, yield 100%.

According to the analysis of related databases, 54962-75-3, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Chinese Academy Of Medical Sciences Pharmaceutical Institute; Xu Boling; Chen Xiaoguang; Cui Guonan; Lai Fangfang; Zhou Jie; Ji Ming; Wang Xiaoyu; Du Tingting; Li Ling; Jin Jing; (144 pag.)CN110483366; (2019); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 7314-86-5,Some common heterocyclic compound, 7314-86-5, name is 1,3,5,7-Tetrabromoadamantane, molecular formula is C10H12Br4, 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.

In a 250ml three-necked flask equipped with a condenser tube5.0 g (ie 11.0 mmol) of tetrabromoadamantane and20 mL (ie, 165 mmol) of m-dibromobenzene,Condenser duct from the upper end connected to an inverted funnel 30% NaOH aqueous solution,To absorb the HBr produced by the reaction.Cold water bath at 5 ,To the reaction system was added 1.2g (ie, 4.5mmol) of AlBr3, stirring was continued under a cold water bath for 1 hour,Then remove the cold water bath,Return to room temperature for about 3 hours,The final reaction system was heated in an oil bath to 60 C for 4 hours,The reaction solution was cooled to room temperature,Pour into 100 mL of acidic ice water and stir for 1 h.After the ice is completely melted, 100 ml of methylene chloride is added to the mixture for extraction. The organic layer is washed with water until neutral, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and the filtrate is concentrated. The concentrated solution is then slowly added dropwise to 100 ml Methanol, precipitation,9.31 g of a pale yellow solid was obtained in a yield of 79%.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1,3,5,7-Tetrabromoadamantane, its application will become more common.

Reference:
Patent; Chinese Academy Of Sciences Physics And Chemistry Technology Institute; Chen Jinping; Li Yi; Yu Tianjun; Zeng Yi; (18 pag.)CN107266319; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 608-30-0, The chemical industry reduces the impact on the environment during synthesis 608-30-0, name is 2,6-Dibromoaniline, I believe this compound will play a more active role in future production and life.

This compound was prepared by modified literature procedures.11,12 A solution of NaNO2 (0.205 g,2.97 mmol) in H2O (1.5 mL) was added dropwise to a suspension of 2,6-dibromoaniline, 7c, (678 mg, 2.70 mmol) in concentrated aqueous HCl (2.6 mL, 12 M) at 0 C. The mixture was stirred at 0 C for 90 min. Additional NaNO2 (55 mg, 0.797 mmol) was added. The mixture was stirred for an additional 45 min at 0 C and then the resulting cold solution was added dropwise to a stirred solution of potassium ethyl xanthate (525 mg, 3.27 mmol) in H2O (0.65 mL) at 45 C through a glass pipet with a plug of glass wool. The reaction mixture was stirred for 30 min at this temperature and then allowed to cool to room temperature. The reaction mixture was extracted with diethyl ether (3×50 mL). The combined organic extracts were washed with 1 M NaOH solution (100 mL), water (3x 50 mL), brine (50 mL), dried over anhyd MgSO4, filtered and evaporated under reduced pressure. The resulting crude product was dissolved in ethanol (8 mL) and heated to reflux. Potassium hydroxide pellets (654 mg, 11.6 mmol) were added and refluxing continued overnight. After cooling to room temperature, the ethanol was evaporated under reduced pressure. The residue was dissolved in water and washed with diethyl ether (100 mL). The aqueous layer was acidified with 1 M HCl to pH 2 and extracted with diethyl ether (3 50 mL). The organic extracts were washed with water (50 mL), brine (50 mL), dried over anhyd MgSO4, filtered and evaporated under reduced pressure. The residue was purifiedby column chromatography on silica gel using hexanes as eluent to give 8b as a slightly yellow solid (518 mg, 72%). This compound always contains trace amounts of oxidized disulfide compound. Therefore, compound 8b was used in next step without further purification. 1H NMR (500 MHz, CD2Cl2) d 5.04 (s, 1H), 6.87 (t, J=7.0 Hz, 1H), 7.52 (d, J=7.0 Hz, 2H); IR (KBr) 1400, 1421, 1543, 2553(SH), 3064, 3458 cm1.

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, 2,6-Dibromoaniline, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Yamamoto, Takuhei; Ammam, Malika; Roberts, Sue A.; Wilson, George S.; Glass, Richard S.; Tetrahedron; vol. 72; 20; (2016); p. 2527 – 2534;,
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. 2695-48-9, name is 8-Bromo-1-octene belongs to bromides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below. HPLC of Formula: C8H15Br

(9RS,12S)-Isomer A Grignard reagent was prepared from 1-bromo-7-octene (6.80 g, 36 mmol) and Mg (1.08 g, 45 mmol) in dry THF (30 mL) in the presence of a small amount (20 mg) of I2 under argon. A solution of (S)-7 (5.77 g, 26 mmol) in dry THF (10 mL) was added dropwise to the ice-cooled and stirred Grignard reagent at 0-10 C. Stirring was continued for 1 h at 0-5 C, and the mixture was left to stand overnight at room temperature. It was then poured into ice and dil HCl, and extracted with Et2O. The Et2O solution was washed successively with water, NaHCO3 solution, and brine, dried (MgSO4), and concentrated in vacuo. The residue (10.9 g) was chromatographed over SiO2 (70 g). Elution with hexane gave 1.0 g of hydrocarbons, and further elution with hexane/EtOAc (20:1) afforded 6.42 g (74%) of (9RS,12S)-8 as a colorless oil, nD25=1.4638; [alpha]D25 +0.16 (c 2.58, hexane); numax (film): 3348 (br m), 3077 (m), 2926 (s), 1641 (m), 1463 (m), 992 (m), 909 (s); deltaH (CDCl3): 0.860 (1.5H, d, J 6.4), 0.865 (1.5H, d, J 6.4), 1.05-1.20 (2H, m), 1.20-1.50 (28H, br m), 2.04 (4H, q-like, J 6.4), 3.55 (1H), 4.925 (2H, d-like, J 10.4), 4.980 (2H, d-like, J 17.2), 5.75-5.88 (2H, m); GC-MS (same conditions as those for 3): tR 23.60 (90.6%, 8), 27.15 min (6.8%, M+=360), MS of (9RS,12S)-8 (EI, 70 eV): m/z: 334 (<1) [M+-2], 318 (4) [(M-H2O)+], 207 (4), 165 (5), 149 (6), 137 (11), 123 (32), 109 (42), 94 (66), 81 (86), 69 (69), 67 (53), 55 (100), 41 (40). HRMS calcd for C23H44O: 336.3392, found: 336.3388. The synthetic route of 2695-48-9 has been constantly updated, and we look forward to future research findings. Reference:
Article; Mori, Kenji; Akasaka, Kazuaki; Matsunaga, Shigeki; Tetrahedron; vol. 70; 2; (2014); p. 392 – 401;,
Bromide – Wikipedia,
bromide – Wiktionary