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Chemical Structure| 244236-52-0 Chemical Structure| 244236-52-0

Structure of 244236-52-0

Chemical Structure| 244236-52-0

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Product Details of [ 244236-52-0 ]

CAS No. :244236-52-0
Formula : C12H18N2O4S
M.W : 286.35
SMILES Code : O=C(C1=C(C)N=C(NC(OC(C)(C)C)=O)S1)OCC
MDL No. :MFCD11976770

Safety of [ 244236-52-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319
Precautionary Statements:P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330

Application In Synthesis of [ 244236-52-0 ]

* 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.

  • Downstream synthetic route of [ 244236-52-0 ]

[ 244236-52-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 7210-76-6 ]
  • [ 24424-99-5 ]
  • [ 244236-52-0 ]
YieldReaction ConditionsOperation in experiment
79% With triethylamine;dmap; In tetrahydrofuran; at 0 - 20℃; To a mixture of ethyl 2-amino-4-methylthiazole-5-carboxylate (5.00 g, 26.80 mmol) and di-te/f-butyl dicarbonate (6.44 g, 29.50 mmol) in anhydrous tetrahydrofuran (200.0 mL) was added triethylamine (2.99 g, 29.50 mmol) and A/,A/-dimethyl-4-aminopyridine (0.30 g, 2.46 mmol) at 0 C. The resulting solution was stirred at ambient temperature for 16 h, acidified to pH ~ 2 with 1 N hydrochloric acid solution and extracted with ethyl acetate (3 x 300 mL). The organic layer was washed with saturated aqueous ammonium chloride solution (250 mL), dried over anhydrous sodium sulphate and filtered. The filtrate was concentrated in vacuo to afford the title compound as anoff-white solid (6.10 g, 79%): 1H NMR (300 MHz, DMSO-cfe) 8 11.87 (s, 1H), 4.21 (q, J = 7.1 Hz, 2H), 2.49 (s, 3H), 1.48 (s,9H), 1.26 (t, J = 7.1 Hz, 2H).
70 - 72% dmap; In tetrahydrofuran; for 18 - 24h; [0261] A suspension of ethyl-2-amino-4-methyl-thiazole-5-carboxylate (18.6 g, 100 mmol), di-t-butyldicarbonate (26.2 g, 120 mmol) and 4-dimethylaminopyridine (800 mg, 6.55 mmol) in dry tetrahydrofuran (300 mL) was stirred under nitrogen for 18 h. The solvent was evaporated in vacuo. The residue was suspended in dichloromethane (1 L) and filtered through a pad of celite. The filtrate was washed with 1 N aqueous HCl solution (300 mL, 2×), water and brine, dried (MgSO4), and concentrated in vacuo. The residue was triturated with hexanes. The solid was filtered and dried in vacuo to obtain the title compound (20 g, 72%) as a tan solid.[0403] A suspension of ethyl-2-amino-thiazole-5-carboxylate (972 mg, 6 mmol, B. Plouvler, C. Bailly, R. Houssin, j-P. Henlchart Heterocyles 32(4), 693-701, 1991 and H. J. Becker, J. de Jonge Rec. Trav. Chim, 61, 463, 1942), di-t-butyldicarbonate (1.94 g, 9 mmol) and 4-dimethylaminopyridine (73 mg, 0.6 mmol) in dry tetrahydrofuran (75 mL) was stirred under nitrogen for 24 h. The solvent was evaporated in vacuo. The residue was suspended in ether (50 mL). The solid was washed with ether (10 mL, 3×), and dried in vacuo to obtain the title compound (1.1 g, 70%).
60% With dmap; In dichloromethane; for 48h; Step 1Compound 25a (4.6 g, 20.66 mmol) was suspended in 100 mL of CH2Cl2. 4-N,N'-dimethylamino pyridine (3.2 g, 26.19 mmol) and to the resulting suspension was added ditertbutyl Bicarbonate (5.64 g, 25.84 mmol). The resulting reaction was allowed to stir for 2 days, then was diluted with 100 mL of CH2Cl2, washed sequentially with a saturated NaHCO3 aqueous solution (50 mL), H2O (50 mL), a 1.0 M HCl aqueous solution (50 mL), H2O (50 mL), and brine (50 mL) The organic solution was dried over Na2SO4, filtered, and concentrated in vacuo to provide 4.02 g of the mono-boc protected product 25b (60%) as a colorless solid.
26.7% With dmap; triethylamine; In tetrahydrofuran; at 20℃; for 12h; To a stirred solution of ethyl 2-amino-4-methylthiazole-5-carboxylate (3) (5.6 g, 30.07 mmol, 1 eq) in THF (50 mL), triethylamine (6.08 g, 60.14 mmol, 2 eq), DMAP (0.367 g, 0.03 mmol, 0.1 eq) and Boc2O (13.12 g, 30.07 mmol, 1 eq) were added at RT. The reaction mixture was stirred at RT for 12 h. The progress of the reaction was monitored by TLC (M.Ph: 10% EtOAc in n-hexane; RfSM: 0.5, RfRM: 0.65). After completion of reaction, the reaction mixture was diluted with water and extracted with ethyl acetate (2 x 500 mL). The combined organic layers was dried over anhydrous sodium sulfate, filtered and concentrated to dryness. The crude was purified through silica gel column chromatography (elution: 0-15% EtOAc in n-hexane) to afford 4 (2.3 g, 26.7%) as an off white solid.1H NMR (400 MHz, DMSO-d6) δ ppm 11.83 (br. s, 1H), 4.22 (q, J = 6.0 Hz, 2H), 2.44 (s, 3H), 1.43 (s, 9H), 1.22 (t, J = 7.6 Hz, 3H). LCMS: 287.13 (M+H)+, Rt = 1.98 min.
With dmap; In tetrahydrofuran; A solution of 5.58 g of methyl 2-amino-4-methylthiazole-5-carboxylate, obtained by the process described in Example 2, in tetrahydrofuran is reacted with 7.19 g of di-tert-butyl dicarbonate and 0.18 g of dimethylaminopyridine to give 6.90 g of a white powder, which is used as it is without purification. LC/MS: MH+=187. NMR 300 MHz (CDC13): 1.45 (s, 9H); 2.48 (s, 3H); 9.80 (broad s, 1H).
To a solution of 1.00 g of 2-amino-4-methyl-thiazole-5-carboxylic acid ethyl ester, 0.957 ml of Et3N, and 1.73 g of di-f-butyl dicarbonate in 30 ml of THF, 65 mg of dimethylaminopyridine are added. After stirring for 2 hours at ambient temperature, the mixture obtained is adjusted to pH 6 by adding 1 N HCI. After exhaustive extraction with EtOAc, the combined organic extracts obtained are dried and concentrated.2-tert-Butoxycarbonylamino-4-methyl-thiazole-5-carboxylic acid ethyl ester is obtained.
With dmap; triethylamine; In tetrahydrofuran; at 20℃; for 18h; Step a. To a solution of ethyl 2-amino-4-methylthiazole-5-carboxylate (10.75 mmol) in THF (15 ml) were added (BOC)20 (12.90 mmol), DMAP (1.07 mmol) and TEA (16.13 mmol) at rt. The reaction mixture was stirred at rt for 18 h. The resulting reaction mixture was diluted with EtOAc (180 ml) and washed with 1M HC1 (100 ml) and brine (100 ml). The organic phase was collected, dried over Na2SC filtered and concentrated under reduced pressure yielding ethyl 2-((tert-butoxycarbonyl)amino)-4-methylthiazole-5-carboxylate (8.39 mmol). This material was used directly for the next step without further purification.

 

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