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CAS No. : | 159451-66-8 | MDL No. : | MFCD06411381 |
Formula : | C10H13BrN2O2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | CKXAMCSVTNPSCZ-UHFFFAOYSA-N |
M.W : | 273.13 | Pubchem ID : | 16217843 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H317-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With N,N,N,N,-tetramethylethylenediamine; hydrogen; catacxium A;palladium diacetate; In tetrahydrofuran; at 100℃; under 3750.38 Torr; for 16h; | 6.0 g (21 .3 mmol) of (5-Bromo-pyridin-2-yl)-carbamic acid tert-butyl ester was dissolved in THF (55 mL). A solution of 4.9 mL (32 mmol) TMEDA, 241 mg (0.64 mmol)CataCxium A, and 48 mg (0.213 mmol) Pd(OAc)2 in THF (5 mL) was added and the mixture was treated with 5 bar synthesis gas at 100 C for 16 h.After cooling, the salts were filter off and the mixture was poured onto water (200 mL). The precipitated was filtered and rinsed with additional water to yield 4.8 g (quant.) HPLC: tR = 1 .2 min (YMC J'sphere ODS H 80 20 x 2.1 mm, 4 muetatauiota, A: H2O + 0.05 % TFA, B: MeCN, 4% - 95 % in 2.45 min, 1 mL/min, 30 C. |
100% | With N,N,N,N,-tetramethylethylenediamine; hydrogen; palladium diacetate; catacxium A; In tetrahydrofuran; at 100℃; under 3750.38 Torr; for 16h; | EXAMPLE 2 (5-Formyl-pyridin-2-yl)-carbamic acid tert-butyl ester 6.0 g (21.3 mmol) of (5-Bromo-pyridin-2-yl)-carbamic acid tert-butyl ester was dissolved in THF (55 mL). A solution of 4.9 mL (32 mmol) TMEDA, 241 mg (0.64 mmol) CataCxium A, and 48 mg (0.213 mmol) Pd(OAc)2 in THF (5 mL) was added and the mixture was treated with 5 bar synthesis gas at 100 C. for 16 h. After cooling, the salts were filter off and the mixture was poured onto water (200 mL). The precipitated was filtered and rinsed with additional water to yield 4.8 g (quant.) HPLC: tR=1.2 min (YMC J'sphere ODS H 80 20*2.1 mm, 4 mum, A: H2O+0.05% TFA, B: MeCN, 4%-95% in 2.45 min, 1 mL/min, 30 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | To a solution of (5-Bromo-pyridin-2-yl)-carbamic acid tert-butyl ester (1.0 g, 3.7 mmol, 1.0 equiv.) in dry THF (12 mL) at 0 C was added a2 M solution of i-PrMgCl in THF (1.85 mL, 3.7 mmol, 1.0 equiv.) during 5 min. The clear solution wasstirred at that temperature for an additional 5 min, and a 2.5 M solution of n-BuLi in hexanes (3 mL,7.5 mmol, 2.0 equiv.) was added dropwise during 5 min, while maintaining the temperature below20 C. The resulting mixture was stirred at that temperature for 0.5 h, dry DMF (0.27 g, 3.7 mmol,1.0 equiv.) in dry THF (5 mL) was added dropwise during 10 min. The resulting mixture was warmedto 20 C in 0.5 h and quenched with water (6 mL). After stirring the mixture below 20 C for 10 min,the phases were separated and the water phase was extracted one additional time with ethyl acetate.The resulting suspension was allowed to reach room temperature and fitered through a 0.5 1 cmpad of silica gel eluted with 10 mL of ethyl acetate. The ltrate was concentrated and the residue waspuried by ash chromatography on silica gel (eluent: petroleum ether/ethyl acetate = 10:1) to affordproduct 3a as white solid, 0.73 g (yield: 90%). 1H-NMR (600 MHz, DMSO) 10.42 (s, 1H), 9.94 (s, 1H),8.93-8.60 (m, 1H), 8.17 (dd, J = 8.8, 2.3 Hz, 1H), 7.99 (d, J = 8.8 Hz, 1H), 1.48 (s, 9H). 13C-NMR (151 MHz,DMSO) 191.18, 157.08, 152.82, 152.40, 138.23, 127.30, 112.23, 80.97, 28.37. |