55899-13-3 | Pyridine-derivatives

The origin of a common compound about 55899-13-3

At the same time, in my other blogs, there are other synthetic methods of this type of compound,55899-13-3, 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate, and friends who are interested can also refer to it.

Synthetic Route of 55899-13-3, 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. 55899-13-3, name is 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate. A new synthetic method of this compound is introduced below.

Methyl 6-[(6-bromo-2-phenylpyrazolo[1,5-a]pyridin-3-yl)carbonyl]pyridine-2-carboxylate After potassium carbonate (6.25 g) was added to an N,N-dimethylformamide (22.6 mL) solution of methyl 6-(1-oxo-3-phenyl-2-propyn-1-yl)pyridine-2-carboxylate (3.00 g) and 1-amino-3-bromopyridinium 2,4,6-trimethylbenzenesulfonate (7.71 g) at room temperature, the mixture was stirred at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was evaporated and then the residue thus obtained was purified by silica gel column chromatography (n-hexane:ethyl acetate = 3:1) to obtain a title compound as a yellow crystal (1.35 g). 1H-NMR (400 MHz, CDCl3) delta 3.85 (3H, s), 7.05 (2H, t, J = 7.9 Hz), 7.13 (1H, t, J = 7.9 Hz), 7.23 (2H, d, J = 7.9 Hz), 7.59 (1H, dd, J = 9.1 and 1.8 Hz), 7.86 (1H, t, J = 7.9 Hz), 7.94 (1H, d, J = 7.9 Hz), 8.00 (1H, dd, J = 7.9 and 1.2 Hz), 8.28 (1H, d, J = 9.1 Hz), 8.73 (1H, d, J =1.8 Hz).

Reference:
Patent; Kyorin Pharmaceutical Co., Ltd.; Kissei Pharmaceutical Co., Ltd.; SETO, Shigeki; UMEI, Kentaro; NISHIGAYA, Yosuke; TANIOKA, Asao; KONDO, Tatsuhiro; KONDO, Atsushi; TATANI, Kazuya; KAWAMURA, Naohiro; EP2669285; (2013); A1;,
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Brief introduction of 55899-13-3

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. 55899-13-3, 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate, other downstream synthetic routes, hurry up and to see.

Related Products of 55899-13-3 ,Some common heterocyclic compound, 55899-13-3, molecular formula is C14H17BrN2O3S, 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.

The reaction was performed using general flow procedure reacting 3-bromopyridine 2a with ethylpropiolate 4b. The outlet solution (195 mL, collected over 51 mins) was stirred at room temperature whiletriethylamine (17.5 mL, 126 mmol) was added followed by ethyl propiolate (9.30 mL, 98.4 mmol). The bright redmixture was stirred at room temperature for 15 minutes was concentrated in vacuo to remove the MeCN and thendiluted with EtOAc (250 mL) and brine (100 mL). The organic layer was separated and the aqueous phase washedtwice more with EtOAc (2 x 200 mL). The combined organic layers were dried over anhydrous sodium sulfate andconcentrated in vacuo to give a dark red oil.The crude material was purified by column chromatography on a 100 g silica column using the Biotage machine anda gradient from 7 to 60 % EtOAc/heptane. 5c eluted first from the column. Pale red solid (1.94 g, 51 min collectiontime, 11 %). 1H NMR (400 MHz, d6-DMSO) (3H, t, J = 4 Hz, CH2CH3), 4.31 (2H, q, J = 4 Hz, CH2CH3), 7.743 SYNLETT: LETTERTemplate for SYNLETT and SYNTHESIS Thieme Stuttgart · New York 2017-04-25 page 3 of 4(1H, d, J = 8 Hz, ArH), 8.01 (1H, d, J = 4 Hz, ArH), 8.47 (1H, s, ArH), 9.31 (1H, s, ArH) ppm. 13C NMR (101 MHz,d6-DMSO) 14.3, 59.8, 103.6, 108.1, 118.9, 130.3, 131.3, 138.6, 144.7, 162.2 ppm. HRMS (FAB) calcd forC10H10O2N2Br 268.99202, found 268.99194/270.98981

Reference:
Article; Brocklehurst, Cara E.; Koch, Guido; Rothe-Poellet, Stephanie; La Vecchia, Luigi; Synlett; vol. 28; 13; (2017); p. 1636 – 1640;,
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Brief introduction of 55899-13-3

Introduction of a new synthetic route about 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate

In contrast to the other examples, only the cyclisation reaction was performed in flow. TheVapourtec R-series was equipped with three pumps. MSH 1 (2 g, 71 % damp solid, 6.60 mmol)1 and 3-bromopyridine 2a (1.04 g, 6.60 mmol) were dissolved together in THF/H2O (1:1, 33 mL, 0.2 M). Triethylamine (0.92mL, 6.60 mmol) dissolved in THF (8.25 mL, 0.8 M) was mixed with the first inlet via a Y-piece with flow rates of2.86 mL/min and 1.07 mL/min respectively (1.5 eq of triethylamine). Methyl propiolate 4a (0.56 g, 6.60 mmol) wasdissolved in THF (8.25 mL, 0.8 M) and introduced in a second Y-piece at flow rate 1.07 mL/min (1.5 eq of methylpropiolate). The system solvent was THF. The PFA reactor coils, with volumes 2 mL and 10 mL respectively, were setto temperatures 30 C and 90 C respectively. The reaction mixture from the first two inlet streams spent 31 secondsresidency time in the first reactor and then 2 minutes residency time in the second reactor. The operating pressure was7.5 bar with 3 pumps. The reaction set-up was flushed afterwards with 33 % HCl (conc.) in MeOH followed by IPA.The total flow rate at the outlet was 5 mL/min. The outlet stream (40 mL, collected over 8 minutes) was concentratedin vacuo to remove the THF and then diluted with EtOAc (250 mL) and brine (100 mL). The organic layer wasseparated and the aqueous phase washed twice more with EtOAc (2 x 200 mL). The combined organic layers weredried over anhydrous sodium sulfate and concentrated in vacuo to give a dark red oil.The crude material was purified by column chromatography on a 100 g silica column using the Biotage machine anda gradient from 7 to 60 % EtOAc/heptane. 5a eluted first from the column. Pale red solid (0.43 g, 8 min collectiontime, 42 %). 1H NMR (400 MHz, d6-DMSO) 4.10 (3H, s, CH3), 7.79 (1H, d, J = 8 Hz, ArH), 8.26 (1H, d, J = 8 Hz,ArH), 8.73 (1H, s, ArH), 9.56 (1H, s, ArH) ppm. 13C NMR (101 MHz, d6-DMSO) 51.2, 103.3, 108.1, 118.8, 130.3,131.4, 138.7, 144.6, 162.6 ppm. HRMS (FAB) calcd for C9H8O2N2Br 254.97637, found 254.97636/256.97421.5b eluted second from the column. Pale yellow solid. (0.14 g, 8 min collection time, 14 %). 1H NMR (400 MHz, d6-DMSO) 3.82 (3H, s, CH3), 7.06 (1H, dd, J = 4 and 4 Hz, ArH), 7.87 (1H, d, J = 4 Hz, ArH), 8.50 (1H, s, ArH), 8.93(1H, d, J = 4 Hz, ArH) ppm. 13C NMR (101 MHz, d6-DMSO) 51.3, 104.7, 109.8, 114.4, 129.8, 132.8, 137.6, 145.6,161.9 ppm. HRMS (FAB) calcd for C9H8O2N2Br 254.97637, found 254.97638/256.97424

Simple exploration of 55899-13-3

Application of 55899-13-3, Adding some certain compound to certain chemical reactions, such as: 55899-13-3, name is 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate,molecular formula is C14H17BrN2O3S, 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 55899-13-3.

Methyl 6-bromo-2-phenylpyrazolo[1,5-a]pyridine-3-carboxylate [0424] A 70% perchloric acid aqueous solution (12.9 mL) was added to a 1,4-dioxane solution (31 mL) of ethyl O-mesitylsulfonylacetohydroxamate (35.7 g) under an argon atmosphere under ice-cooling, and then the mixture was stirred for 30 minutes under ice-cooling. Ice water (360 mL) was added to the reaction solution, the precipitated solid was filtered off, the obtained solid was dissolved in dichloromethane (104 mL), and the solution was divided into layers. The organic layer was dried over anhydrous magnesium sulfate and filtered off. A dichloromethane solution (104 mL) of 3-bromopyridine (10 mL) was added to the obtained filtrate under ice-cooling, the mixture was stirred at room temperature for 1 hour, and the reaction solution was evaporated to obtain a crude product N-amino-3-bromopyridinium 2,4,6-trimethylbenzenesulfonate. Methyl phenylpropiolate (7.7 mL) and potassium carbonate (28.7 g) were added to an N,N-dimethylformamide solution (104 mL) of the crude product N-amino-3-bromopyridinium 2,4,6-trimethylbenzenesulfonate at room temperature under an argon atmosphere, and then the mixture was stirred at room temperature for 16 hours. Water was added to the reaction solution and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The solvent was evaporated and then the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate = 4:1) to obtain a title compound as a yellow powder (8.0 g).

Simple exploration of 55899-13-3

According to the analysis of related databases, 55899-13-3, the application of this compound in the production field has become more and more popular.

Related Products of 55899-13-3, Adding some certain compound to certain chemical reactions, such as: 55899-13-3, name is 1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate,molecular formula is C14H17BrN2O3S, 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 55899-13-3.

According to the analysis of related databases, 55899-13-3, the application of this compound in the production field has become more and more popular.