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Chemical Structure| 55899-13-3 Chemical Structure| 55899-13-3

Structure of 55899-13-3

Chemical Structure| 55899-13-3

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Product Details of [ 55899-13-3 ]

CAS No. :55899-13-3
Formula : C14H17BrN2O3S
M.W : 373.27
SMILES Code : BrC1=C[N+](N)=CC=C1.O=S(C2=C(C)C=C(C)C=C2C)([O-])=O
MDL No. :MFCD28502700
InChI Key :CMDGFAPRZQBXJY-UHFFFAOYSA-M
Pubchem ID :12208479

Safety of [ 55899-13-3 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 55899-13-3 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Upstream synthesis route of [ 55899-13-3 ]
  • Downstream synthetic route of [ 55899-13-3 ]

[ 55899-13-3 ] Synthesis Path-Upstream   1~3

  • 1
  • [ 626-55-1 ]
  • [ 36016-40-7 ]
  • [ 55899-13-3 ]
YieldReaction ConditionsOperation in experiment
100%
Stage #1: at 30℃; for 0.0166667 h; Flow reactor
Stage #2: With sodium hydroxide In N,N-dimethyl-formamide at 30℃; for 0.0433333 h; Flow reactor
General procedure: All reactions were performed using a commercially available Vapourtec R-series set-up equipped with four pumps.(E)-Ethyl N-(mesitylsulfonyl)oxyacetimidate 7 was dissolved in MeCN (1M) and filtered. Perchloric acid (neat, 11.6M) was mixed with the first inlet via a Y-piece with flow rates of 1.228 mL/min and 0.106 mL/min respectively.Pyridine 2 was dissolved in MeCN (2M), filtered and introduced in a second Y-piece at flow rate 0.614 mL/min.Sodium hydroxide (1 M) was diluted with DMF to 0.667 M and introduced in a third Y-piece at flow rate 1.840mL/min. The stoichiometric ratio of all four inlets was 1:1:1:1. The system solvent was MeCN for the first threeinlets and H2O/DMF (2:1) for the fourth inlet. The PFA (polyfluoroalkoxy alkane polymer) reactor coils, withvolumes 20 mL, 2 mL and 10 mL respectively, were all set to temperature 30 °C. The reaction mixture from the firsttwo inlet streams spent 15 minutes residency time in the first reactor, the second 1.02 minutes and the third 2.64minutes.In all cases the power trace for the third reactor (where amination was occurring) showed that an exotherm took place(less power was required to heat to 30 °C). The operating pressure was 7-8 bar at beginning with just the first twopumps and rose to 9-10 bar with all 4 pumps. The reaction set-up was flushed afterwards with 33 percent aq. HCl (conc.)in MeOH followed by IPA. The total flow rate at the outlet was 3.788 mL/min.1-Amino-3-bromopyridin-1-ium 2,4,6-trimethylbenzenesulfonate (3a): The reaction was performed using generalflow procedure reacting 3-bromopyridine 2a with MSH 1. The outlet solution (25 mL, collected over 3.6 mins) wasconcentrated in vacuo to give an orange solid (3.6 mins collection time, >99percent). 1H NMR (400 MHz, d6-DMSO)2.18 (9H, s, 3 x CH3), 6.77 (2H, s, NH2), 7.93 (1H, dd, J = 4 and 8 Hz, ArH), 7.95 (s, 2H, ArH), 8.49 (1H, d, J = 8Hz, ArH), 8.81 (1H, d, J = 8 Hz, ArH), 9.17 (1H, s, ArH) ppm. 13C NMR (101 MHz, d6-DMSO) 20.3, 22.7, 121.4,128.6, 129.9, 135.8, 136.4, 138.6, 141.4, 142.5, 166.0 ppm. HRMS (FAB) calcd for C5H6BrN2+ 172.97144, found172.97105 and C9H11O3S- 199.04289 found 199.04277. DSC showed small exotherm with 61 J/g onset 249 °C andlarger exotherm with 573 J/g onset 299 °C.
References: [1] Synlett, 2017, vol. 28, # 13, p. 1636 - 1640.
[2] Chemical and Pharmaceutical Bulletin, 1981, vol. 29, # 12, p. 3696 - 3705.
[3] Tetrahedron, 1981, vol. 37, p. 1787 - 1794.
[4] Russian Journal of Organic Chemistry, 2011, vol. 47, # 6, p. 897 - 903.
  • 2
  • [ 626-55-1 ]
  • [ 38202-27-6 ]
  • [ 55899-13-3 ]
References: [1] Patent: EP2669285, 2013, A1, . Location in patent: Paragraph 0423; 0424.
  • 3
  • [ 55899-13-3 ]
  • [ 922-67-8 ]
  • [ 1062368-71-1 ]
  • [ 1062368-70-0 ]
YieldReaction ConditionsOperation in experiment
42%
Stage #1: With triethylamine In tetrahydrofuran; water at 30℃; for 0.00861111 h; Flow reactor
Stage #2: at 90℃; for 0.0333333 h; Flow reactor
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 percent 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 percent 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 percent EtOAc/heptane. 5a eluted first from the column. Pale red solid (0.43 g, 8 min collectiontime, 42 percent). 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 percent). 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
References: [1] Synlett, 2017, vol. 28, # 13, p. 1636 - 1640.
 

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