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Chemical Structure| 149587-72-4

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Product Details of [ 149587-72-4 ]

CAS No. :149587-72-4
Formula : C11H15NO4S
M.W : 257.31
SMILES Code : O=C(C1=C(NC(OC(C)(C)C)=O)C=CS1)OC
MDL No. :MFCD01763684
InChI Key :JEMOHNKXRFEUDT-UHFFFAOYSA-N
Pubchem ID :18925408

Safety of [ 149587-72-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H317
Precautionary Statements:P280

Application In Synthesis of [ 149587-72-4 ]

* 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 [ 149587-72-4 ]

[ 149587-72-4 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 149587-72-4 ]
  • [ 101537-64-8 ]
YieldReaction ConditionsOperation in experiment
97% With water monomer; sodium hydroxide; In tetrahydrofuran; at 70℃; for 12h; Compound 2 (2158 mg, 8.40 mmol) was dissolved in THF (10 mL), NaOH solution (8.2 mL, 4 M, 33.60 mmol) was added with stirring, and the temperature was raised to 70 C. to react for 12 h. After TLC monitoring reaction, add HCl (4M) to adjust pH to 2, distill under reduced pressure until a large amount of solid is precipitated, and dry after suction filtration to obtain corresponding product 3 (1.98g), white solid, melting point: 152C, yield 97%.
13.8 g (97%) With sodium hydroxide; In tetrahydrofuran; Method B 3-t-Butoxycarbonylaminothiophene-2-carboxylic acid Methyl 3-t-butoxycarbonylaminothiophene-2-carboxylate (15.0 g, 58.3 mmol) was warmed in a mixture of 1 N sodium hydroxide (116.6 ml) and tetrahydrofuran (60 ml) at 50 C. for 16 hours. The mixture was evaporated to a volume of approximately 60 ml, and acidified (pH=2) with hydrochloric acid under cooling in an ice bath. The precipitate was filtered off, washed with water, and dried to afford 13.8 g (97%) of 3-t-butoxycarbonylaminothiophene-2-carboxylic acid. M.p. 168-169 C. Litt. m.p. 168-169 C. (i. Chem. Res. (S), 296, 1985). 1 H-NMR (DMSO-D6, δ): 1.49 (s, 9H), 7.76 (d, 1H), 7.85 (d, 1H), 9.45 (s, 1H), 13.45 (s, 1H).
A mixture of methyl 3-amino-2-thiophene-carboxylate (2.53 g, 15.9 mmol), Boc2O (7.64 g, 35 mmol), and DMAP (2.04 g, 16.7 mmol) was dissolved in acetone (15 mL) and TEA (5 mL). The reaction mixture was stirred vigorously for 4 h and diluted to a volume of 75 mL with dichloromethane. The resulting solution was washed with cold 1 N HCl (3×50 mL), 1 N NaOH (3×50 mL), and brine (50 mL). The dichloromethane solution was then dried over MgSO4, filtered, and concentrated in vacuo to yield a yellow oil. The crude product was loaded onto a short plug of silica and eluted with 9:1 hexanes/ethyl acetate to yield a pale yellow solid (1.2 g) that was used without further purification. The solid was dissolved in methanol (76 mL) and 50% NaOH (4 mL) and the mixture was stirred for 4 h. The reaction was diluted to a volume of 160 mL with water and concentrated briefly in vacuo. The remaining aqueous solution was washed with diethyl ether (2×80 mL), cooled in an ice bath, and cautiously acidified to pH 2 with sulfuric acid. The suspension was washed with ethyl acetate (3×50 mL) and the combined organic washes were dried over MgSO4, filtered, and concentrated in vacuo to yield (11) as a white solid (0.79 g) in 69% yield over two steps. 1H NMR (DMSO-d6) δ 9.43 (s, 1H), 7.80 (d, J=5.4 Hz, 1H), 7.72 (d, J=5.4 Hz. 1H), 1.46 (s, 9H); 13C NMR (75 MHz, DMSO-d6) δ165.8, 151.8, 144.9, 133.1, 121.2, 109.9, 81.5, 28.6; EI-MS mae 243.0563 (M+calculated 243.0565 for C10H13NO4S).
With sodium hydroxide; In ethanol; water monomer; at 20℃; for 1h; To a mixture of methyl 3-amino-2-thiophenecarboxylate (8 g, 51 mmol) and BOC2O (11 g, 50 mmol) in CH2Cl2 (400 ml) was added 4-(dimethylamino)pyridine (1 g, 8.1 mmol). The reaction was stirred at RT overnight and washed with 1N HCl (100 ml), followed by water and brine.The organic layer was dried over Na2SO4 and evaporated under reduced pressure and used for the next step without further purification.To the residue (2 g, ~7 mmol) in EtOH (50 ml) was added 1N NaOH (25 ml), the reaction was stirred at RT for 1 h and the solvent was evaporated under reduced pressure.water (5 ml) was added and the solution was acidified with HOAc. The precipitate was filtered and used in the next step without further purification. MS (ES-): 242 (M-H)-.
Methyl 3-[(tert-butoxycarbonyl)amino]thiophene-2-carboxylate (32 g, 124.4 mmol) (step 1) was dissolved with methanol (140 mL) and sodium hydroxide was added (IN, 190 mL). The mixture was stirred at 50 0C for 16 h. Some starting material was remaining by TLC and so additional sodium hydroxide was added (1.7N, 275 mL) and the mixture was stirred at 50 0C for 2 h. The mixture was cooled to rt and acidified to pH 5 with HCl (IN). Solids were filtered out and combined with the solid remaining after extraction with EtOAc, drying with Na2SO4, and evaporation. The product was used without further purification.

  • 2
  • [ 149587-72-4 ]
  • [ 942589-45-9 ]
 

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