Tag: M.W=200-300

Synthetic Route of 50594-82-6, 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. 50594-82-6, name is 3,4,5-Trichlorobenzotrifluoride, This compound has unique chemical properties. The synthetic route is as follows.

(b) Preparation by a known process, using sodium hydroxide as the base 358 g (1.5 mol) of 3,4,5-trichloro-benzotrifluoride were added dropwise to a mixture of 330 g (3 mol) of resorcinol and 60 g (1.5 mol) of sodium hydroxide in 2 liters of dimethylsulphoxide at 120-130 C. in the course of 7 hours. Thereafter, the reaction mixture was stirred at 130 C. for 8 hours. After cooling to room temperature, the reaction mixture was stirred into a solution of 80 g of sodium hydroxide in 7 liters of water. The insoluble portion was separated off and taken up in toluene; according to the thin layer chromatogram, this solution contained no 2,6 -dichloro-4-trifluoromethyl-3′-hydroxydiphenyl ether. In order to work up the aqueous phase, it was acidified with hydrochloric acid and the oil which separated out was extracted with toluene. After drying, the solvent was stripped off and the residue was distilled. 30 g (6.7% of theory) of 2,6-dichloro-4-trifluoromethyl-3′-hydroxydiphenyl ether were obtained in this manner. Boiling point 123-130 C./0.15 mm Hg.

The chemical industry reduces the impact on the environment during synthesis 3,4,5-Trichlorobenzotrifluoride. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Bayer Aktiengesellschaft; US4264769; (1981); A;,
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Application of 81927-55-1, 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. 81927-55-1 name is Benzyl 2,2,2-trichloroacetimidate, 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.

To a solution of methyl (3R)-3-hydroxybutanoate (10 g) and benzyl 2,2,2-trichloroethanimidate (23.6 g) in CH2CI2 (300 mL) was added CF3SO3H (7.2 g) and the mixture was stirred at 25C for 12 h. The reaction mixture was concentrated under reduced pressure to remove CH2CI2. The residue was diluted with water (100 mL), extracted with four times with ethyl acetate (90 mL) and concentrated under reduced pressure. The residue was purified by column chromatography (5i02, petroleum ether / ethylacetate, 20:1 to 9:1) to give methyl (3R)-3-benzyloxybutanoate (10 g, 56.7%) as colorless oil. LCMS:209.1 (M÷Hi

At the same time, in my other blogs, there are other synthetic methods of this type of compound, Benzyl 2,2,2-trichloroacetimidate, and friends who are interested can also refer to it.

Reference:
Patent; FLAGSHIP PIONEERING INNOVATIONS V, INC.; CASEY, John P.; BERRY, David; CASTRO, Alfredo; TAYLOR, Steven J.; MASSARI, Ferdinand E.; PROUSFOOT, John; BOGART, Elijah; BRIGGS, Timothy F.; (211 pag.)WO2018/226732; (2018); A1;,
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Reference of 1127-85-1,Some common heterocyclic compound, 1127-85-1, name is 2,4-Dichloro-5,6,7,8-tetrahydroquinazoline, molecular formula is C8H8Cl2N2, 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.

This was prepared from MA2-10 (0.114 g) and MA3-034 (0.102 g) using procedure B (reaction time, 4 days). The volatiles were evaporated under the reduced pressure and the product was purified via column chromatography (Si02) eluting with hexanes/EtOAc (1:9 to 1 :2 v/v) to give the title compound MA3-064-1 as a gray solid (0.087 g, 44%). Mp: 265 C (dec). lH NMR (400 MHz, DMSO-ifc): delta 9.67 (s, 1H, disappeared on D20 shake), 8.73 (s, 1H, disappeared on D20 shake), 7.56 (s, 1H), 7.26-7.22 (m, 2H), 7.02-6.98 (m, 1H), 2.62 (t, / = 6.1 Hz, 2H), 2.47-2.43 (m, 2H, partially overlapped by residual DMSO solvent signal), 1.81-1.73 (m, 4H), 1.30 (s, 9H). NMR (400 MHz, CD3OD) delta 7.73-7.70 (m, 1H), 7.27-7.24 (m, 2H), 7.11-7.05 (m, 1H), 4.63 (s, 1H), 2.69 (t, / = 6.0 Hz, 3H), 2.55 (t, / = 6.0 Hz, 2H), 1.92-1.86 (m, 4H), 1.39 (s, 19H). HPLC-MS (ESI+): m/z 397.2 [40%, (M37C1+H)+], 395.2 [100%, (M35C1+H)+]. Procedure B A mixture of substituted 2,4-dichloropyrimidine (1.0 equiv.), and substituted aniline (1.0-1.05 equiv.), and DIPEA (1.2 equiv.) in isopropanol (0.1 M) was stirred and heated at reflux. The reaction time, work-up, and product isolation procedure are described below.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2,4-Dichloro-5,6,7,8-tetrahydroquinazoline, its application will become more common.

Reference:
Patent; H. LEE MOFFITT CANCER CENTER & RESEARCH INSTITUTE, INC.; SCHOeNBRUNN, Ernst; LAWRENCE, Nicholas J.; LAWRENCE, Harshani R.; (293 pag.)WO2017/66428; (2017); A1;,
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Electric Literature of 1996-29-8,Some common heterocyclic compound, 1996-29-8, name is 1-Bromo-4-chloro-2-fluorobenzene, molecular formula is C6H3BrClF, 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.

1-bromo-4-chloro-2-fluorobenzene (61 g, 291 mmoles), 2,6-dimethoxyphenylboronic acid (50.4 g, 277 mmoles), K2 CO3 (60.4 g, 437 mmoles) and Pd (PPh3) 4 (10.1 g, 8.7 mmoles)Put in a round bottom flask,And then dissolved in 500 ml of THF and 200 ml of distilled water,And the solution was refluxed and stirred at 60 C for 12 hours.When the reaction is complete,The aqueous layer was removed and passed through column chromatography (hexane: DCM 20%)Process the remainder to obtain 38 grams of intermediate 1(51%).

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-4-chloro-2-fluorobenzene, its application will become more common.

Reference:
Patent; SAMSUNG SDI CO., LTD.; Kang, Dong Min; Kim, Jun Seok; Lui, Jinhyun; Lee, Byoungkwan; Lee, Sangshin; Won, Jonswoo; Lee, Namheon; Jung, Sung Hyun; Jung, Ho Kuk; (107 pag.)TW2019/43698; (2019); A;,
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Synthetic Route of 18282-59-2, These common heterocyclic compound, 18282-59-2, name is 4-Bromo-1,2-dichlorobenzene, 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.

Method C; (3,4-Dichloro-phenyl) -(2,2,6,6-tetramethyl-piperidin-4-yl)-amine hydrochloric acid salt; A mixture of 4-amino-2,2,6,6-tetramethylpiperidine (3.4 ml, 20 mmol), potassium tert- butoxide (4.5 g, 40 mmol), 3,4-dichlorobromobenzene (4.97 g, 22 mmol), palladacycle (100 mg, 0.11 mmol) and dioxane (100 ml) was stirred at reflux for 2 h. Water (100 ml) was added and the mixture was extracted with diethyl ether (2 x 50 ml). Chromatography on silica gel with dichloromethane, methanol and conc. ammonia (89:10:1) gave the title compound. Yield 5.56 g, (82 percent). Hydrochloric acid in ether (6.5 ml, 3.1 M) was added and the hydrochloric acid salt was precipitated and stirred for 10 min, followed by filtration. Mp >300°C.

The synthetic route of 18282-59-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; NeuroSearch A/S; WO2005/123679; (2005); A2;,
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These common heterocyclic compound, 13526-66-4, name is 3-Bromo-6-chloroimidazo[1,2-b]pyridazine, 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. COA of Formula: C6H3BrClN3

In an inert atmosphere, 3.0 g (12.9 mmol) of 3-bromo-6-chloroimidazo[1 ,2-b]- pyridazine, 6.85 g (16.8 mmol) of the crude 2-stannylfuro[3,2-b]pyridine, 246 mg (1 .29 mmol) copper (I) iodide and 453 mg (0.645 mmol) bis(triphenylphosphine) palladium(ll)chloride in 100 mL of THF was stirred over night at 85C in a sealed pressure tube. The solvent was evaporated, the obtained solid was digested in dichloromethane/methanol and filtered off. The solid was washed with methanol and hexane to give 2 g of the title compound as solid material.

The synthetic route of 3-Bromo-6-chloroimidazo[1,2-b]pyridazine has been constantly updated, and we look forward to future research findings.

Reference:
Patent; BAYER PHARMA AKTIENGESELLSCHAFT; EIS, Knut; PUeHLER, Florian; ZORN, Ludwig; SCHULZE, Volker; SUeLZLE, Detlev; LIENAU, Philip; HAeGEBARTH, Andrea; PETERSEN, Kirstin; BOeMER, Ulf; WO2013/149909; (2013); A1;,
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Electric Literature of 13918-92-8, A common heterocyclic compound, 13918-92-8, name is 2,4-Difluorobenzene-1-sulfonyl chloride, molecular formula is C6H3ClF2O2S, 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.

Reference Example 143; tert-butyl ({5- (2-cyanopyridin-3-yl) -l-[ (2,4- difluorophenyl) sulfonyl] -lH-pyrrol-3-yl}methyl)methylcarbamate; To a suspension of sodium hydride (60% in oil, 26.0 mg) in tetrahydrofuran (3 mL) was added tert-butyl {[5- (2- cyanopyridin-3-yl) -lH-pyrrol-3-yl]methyl Jmethylcarbamate (156 mg) at room temperature, and the mixture was stirred for 15 min. After stirring, 15-crown-5 (143 mg) and 2,4- difluorobenzenesulfonyl chloride (159 mg) were added dropwise and the mixture was further stirred at room temperature for 1 hr. Saturated aqueous ammonium chloride solution was added, and the mixture was concentrated under reduced pressure. The residue was extracted with ethyl acetate. The separated aqueous layer was extracted again with ethyl acetate. The combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9: 1-*2: 1) to give the title compound as a colorless oil (yield 208 mg, 85%).1H-NMR (CDCl3) delta: 1.48(9H,s), 2.85 (3H,brs) , 4.29 (2H,brs) , 6.46(lH,brs) , 6.80-6.88 (IH,m) , 6.93 (lH,ddd, J=IO.2, 8.1, 2.4Hz) , 7.20(lH,ddd, J=8.8, 8.0, 5.8Hz) , 7.46 (IH, s) , 7.55(lH,dd, J=7.9,4.7Hz) , 7.93 (IH, dd, J=8.0, 1.6Hz) , 8.69(lH,dd, J=4.7,1.7Hz) .

The synthetic route of 13918-92-8 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; TAKEDA PHARMACEUTICAL COMPANY LIMITED; WO2008/108380; (2008); A2;,
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Reference of 468075-00-5,Some common heterocyclic compound, 468075-00-5, name is 2-Bromo-1-chloro-4-(trifluoromethoxy)benzene, molecular formula is C7H3BrClF3O, 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 mixture of 2-bromo-l-chloro-4-(trifluoromethoxy)benzene (5.00 g, 18.15 mmol), Pd(dppf)Cl2.CH2Cl2 (1.48 g, 1.82 mmol) and Et3N (5.51 g, 54.45 mmol) in EtOH (30 mL) was degassed, and refilled with CO. The reaction was stirred under CO (50 psi) for 16 hours at 80 C, at which point the desired product was observed by LCMS. The reaction mixture was diluted with EtOH (20 mL), and filtered through a Celite pad. The filtrate was concentrated. The residue was purified by flash chromatography on silica gel (EtOAc in PE = 0% 5%) to afford compound 12-b (2.40 g, 8.93 mmol) as an oil. 1H NMR (400MHz, CDC13) deltaH = 7.66 – 7.59 (m, 1H), 7.42 (d, 1H), 7.24 – 7.19 (m, 1H), 4.36 (q, 2H), 1.35 (t, 3H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2-Bromo-1-chloro-4-(trifluoromethoxy)benzene, its application will become more common.

Reference:
Patent; PRAXIS PRECISION MEDICINES , INC.; REDDY, Kiran; MARTINEZ BOTELLA, Gabriel; GRIFFIN, Andrew, Mark; MARRON, Brian, Edward; (244 pag.)WO2018/148745; (2018); A1;,
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Electric Literature of 108649-59-8, 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. 108649-59-8 name is 1-(2-Bromoethyl)-2,4-dichlorobenzene, 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: Magnesium turnings (13.2 g, 0.55 mol) were placed in dry THF (25 mL) undernitrogen. A small amount (10 mL) of (2-bromoethyl)benzene (92.5 g, 0.50 mol) dissolvedin dry THF (300 mL), added to the magnesium slurry and stirred for a few minutes withwarming until the reaction commenced. The remainder of the (2-bromoethyl)benzenesolution was added dropwise to maintain reflux over an hour, then the reaction mixturewas aged at reflux for an additional an hour. The reaction mixture was cooled to 25 C. In a separate flask, diethyl oxalate (88.2 g, 0.6 mol) was dissolved in dry THF (100mL) and cooled to -10 C. The supernatant solution of (2-phenylethyl)magnesiumbromide was sucked under nitrogen through a sintered-glass filter into a dropping funnel.The reaction temperature was held at -10 C as the solution of Grignard reagent wasadded dropwise over an hour to the diethyl oxalate. The sintered-glass funnel anddropping funnel were then rinsed with dry THF (100 mL), and the rinse was added to thebatch. The reaction mixture was allowed to stand for 30 min and then quenched byaddition of 3 M HCl (145 mL).Hexane (500 mL) was added, and the aqueous layer was discarded. The organicphase was washed with brine (100 mL) and saturated NaHCO3 (100 mL), until theaqueous layer measured to pH 5.0. The organic phase was dried with anhydrous Na2SO4.Filtered and washed with hexane, and the combined layers were concentrated to an oil invacuum. The crude keto ester (103.0 g) was vacuum distilled at 105-110 C (0.2-0.3 mmHg) to afford a colourless oil 90.0 g with 60% yield.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-(2-Bromoethyl)-2,4-dichlorobenzene, and friends who are interested can also refer to it.

Reference:
Article; Zhu, Lufeng; Chen, Houhe; Meng, Qinghua; Fan, Weizheng; Xie, Xiaomin; Zhang, Zhaoguo; Tetrahedron; vol. 67; 34; (2011); p. 6186 – 6190;,
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Application of 19752-55-7, 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. 19752-55-7, name is 1-Bromo-3,5-dichlorobenzene, This compound has unique chemical properties. The synthetic route is as follows.

A 250 ml round-bottom flask was argonated and consecutively charged with Et2O (60 ml), Mg (1.31 g; 54.0 mmol), I2(one crystal), and a solution of 1-bromo-3,5-dichlorobenzene (12.54 g; 55.5 mmol) in Et2O (60 ml) was added in ca. 5 ml portions over 45 min. Stirring was continued for 3 h at RT, and a solution of 9c (9.52 g; 18.0 mmol) in hot toluene (60 ml, ca. 90 °C) was added slowly, and the mixture was heated to 40 °C for 15 h. A precipitate was decanted, washed with toluene (2 30 ml), treated with concd HClaq. (100 ml) at reflux for 3 h, and cooled to RT. The resulted precipitate was filtered, washedwith concd HClaq. (2 30 ml), and dried. Then, most of the beige solid was dissolved in a hot mixture of water (40 ml), concd HClaq. (120 ml) and ethanol (30 ml), resulted solution was decanted, cooled to RT, and part of the solvent (ca. 50 ml) wasslowly evaporated under reduced pressure. The resulted suspension was filtered, and collected filtrate was washed with concdHClaq. (2 30 ml), and dissolved in CH2Cl2 (150 ml). The organic phase was washed with brine (100 ml), and dried overMgSO4. Then, the mixture was filtered, n-heptane (40 ml) was added, and the mixture was slowly evaporated at 300 mbar (very slow rotations, no heating bath applied). The resulted precipitate was filtered, washed with n-hexane, and dried in vacuo. Filtrate was evaporated and the crystallization procedure was repeated. Both crops were collected and combined to obtain 10c (6.70 g; 9.07 mmol; 50percent calculated as a bromide) as a white solid.

The chemical industry reduces the impact on the environment during synthesis 1-Bromo-3,5-dichlorobenzene. I believe this compound will play a more active role in future production and life.

Reference:
Article; Grudzie?, Krzysztof; Basak, Tymoteusz; Barbasiewicz, Micha?; Wojciechowski, Tomasz M.; Fedory?ski, Micha?; Journal of Fluorine Chemistry; vol. 197; (2017); p. 106 – 110;,
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