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Chemical Structure| 501082-56-0 Chemical Structure| 501082-56-0

Structure of 501082-56-0

Chemical Structure| 501082-56-0

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Product Details of [ 501082-56-0 ]

CAS No. :501082-56-0
Formula : C7H9NO2S
M.W : 171.22
SMILES Code : O=C(C1=CC(N)=C(C)S1)OC
MDL No. :MFCD14694722
InChI Key :ZTTXAKCLKGBDIR-UHFFFAOYSA-N
Pubchem ID :59640747

Safety of [ 501082-56-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335-H302+H312+H332
Precautionary Statements:P280-P280-P301+P312-P280-P280-P301+P312

Application In Synthesis of [ 501082-56-0 ]

* 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 [ 501082-56-0 ]

[ 501082-56-0 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 56921-01-8 ]
  • [ 501082-56-0 ]
YieldReaction ConditionsOperation in experiment
99.8% With hydrogen;palladium 10% on activated carbon; In ethyl acetate; under 2585.81 Torr; 5-Methyl-4-nitro-thiophene-2-carboxylic acid methyl ester [15.09 g. , 75.0 mM, Intermediate (23) ] is dissolved in ethyl acetate (200 ML) to which 10% palladium on charcoal (1.03 g) is added and the mixture is shaken under 50 psi of hydrogen. The catalyst is removed by filtration and the solvent is removed leaving 4-amino-5-methyl-thiophene-2-carboxylic acid methyl ester [12. 82 g., 99.8%, Intermediate (24) ] as A YELLOW SOLID ; MS 171.9 (100%, M + 1).
72% With hydrogen;palladium 10% on activated carbon; In tetrahydrofuran; methanol; at 50℃; under 2250.23 Torr; for 8.0h; A mixture of <strong>[56921-01-8]methyl 5-methyl-4-nitrothiophene-2-carboxylate</strong> (95 g) and 10% palladium-carbon (50% containing water, 10 g) in tetrahydrofuran (250 mL)-methanol (250 mL) was stirred at 50C for 8 hr under a hydrogen atmosphere (0.3 MPa). The catalyst was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was crystallized from diethyl ether to give methyl 4-amino-5-methylthiophene-2-carboxylate (58 g, yield 72%) as yellow crystals. melting point 91C.
With sodium hydrogensulfite; In tetrahydrofuran; water; at 20℃; for 8.0h; a) Commercially available compound 40. 1 (10 mmol) in THF (50 mL) is treated with sodium hydrosulfite (50 mmol) in water (20 mL). After 8 hours at room temperature, the reaction is extracted with ethyl acetate (100 mL), and the organic extract is washed with water and brine, dried over anhydrous magnesium sulfate and filtered to give the crude compound 40. 2.
With hydrogen;Raney nickel; In methanol; under 2068.65 Torr; for 16.0h; A mixture of 5-methyl-4-nitrothiophene 2-carboxylic acid methyl ester (2.0 g) in 20 mL of methanol andl mL of a slurry of 50% Raney nickel in water was shaken under 40 psi of hydrogen gas for 16h. The reaction mixture was filtered through diatomaceous earth and the resulting aminothiophene was taken on without further purification.
With hydrogen;Raney Ni; In tetrahydrofuran; methanol; at 20℃; under 760.051 Torr; for 36.0h; To a solution of <strong>[56921-01-8]methyl 5-methyl-4-nitrothiophene-2-carboxylate</strong> (F-3) (14.8 g, 73.6 mmol) in MeOH/THF (1 : 1 , 300 mL) was added Raney Ni. The reaction mixture was degassed and charged with hydrogen 3 times, and then stirred at room temperature for 36 h under 1 atmosphere of hydrogen. Raney Ni was filtered, and the filtrate was concentrated. The residue was treated with aqueous HCI (1 N, 150 mL) and filtered. The filtrate was treated with aqueous NaOH (1 N) to bring pH to about 8 to 9. Then the mixture was extracted with ethyl acetate. The combined organic layers were dried over Na2S04, and the solvent was removed to give the title compound (8.1 g).
Methyl 4-amino-5-methylthiophene-2-carboxylate (F-4) To a solution of <strong>[56921-01-8]methyl 5-methyl-4-nitrothiophene-2-carboxylate</strong> (F-3) (14.8 g, 73.6 mmol) in MeOH/THF (1:1, 300 mL) was added Raney Ni. The reaction mixture was degassed and charged with hydrogen 3 times, and then stirred at room temperature for 36 h under 1 atmosphere of hydrogen. Raney Ni was filtered, and the filtrate was concentrated. The residue was treated with aqueous HCl (1 N, 150 mL) and filtered. The filtrate was treated with aqueous NaOH (1 N) to bring pH to about 8 to 9. Then the mixture was extracted with ethyl acetate. The combined organic layers were dried over Na2SO4, and the solvent was removed to give the title compound (8.1 g).
6.7 g With palladium on activated charcoal; hydrogen; In ethyl acetate; at 22 - 26℃; under 2585.81 Torr; The title compound was prepared by hydrogenation of methyl 5-methyl-4- nitrothiophene-2-carboxylate (8 g, 39.80 mmol) in ethyl acetate (150 ml) in thepresence of catalytic amount of palladium on carbon under 50 psi of hydrogen pressure at room temperature. The reaction mixture was filtered and removed the solvent under reduced pressure to yield 6.7 g of the product as off-white solid. ‘H NIVIR (300 MHz, CDC13) ö 2.25 (s, 3H), 3.00 (s, 2H), 3.83 (s, 3H), APCI-MS (m/z) 172 (M+H).
With aluminum (III) chloride; iron; In methanol; water; for 6.0h;Reflux; The steps are:5-methyl-4-nitro - thiophene-2-carboxylate (3.34g, 16.6mmol) was dissolved inmethanol (25 mL) and water (10mL) in a mixed solvent was added ammoniumchloride (4.39g, 82mmol), reduced iron powder (4.2g, 75mmol), stirred at refluxfor 6 hours. Cooled to room temperature, filtered under reduced pressure, thefiltrate was concentrated, and the residue was dissolved in ethyl acetate plusSolution, washed with water, brine, dried, and concentrated to dryness to give4-amino-5-methyl - thiophene-2-carboxylic acid methyl ester The crude (2.1g,74%). ESI-MS: m / z 172 (M + H).
17.1 g With hydrogen; In tetrahydrofuran; methanol; [0512] Methyl 5-methyl-4-nitrothiophene-2-carboxylate (24.3 g) was dissolved in a mixture of THF (100 mL) and methanol (100 mL) and then to this solution was added wet Raney Ni. The solution was degassed, refilled with hydrogen, and stirred over an atmosphere of hydrogen overnight. The mixture was filtered through a pad of Celite and concentrated to give the title product (17.1 g), which was used directly in the next synthetic step. LC (method A): tR = 0.55 mm. LC/MS (El) m/z. [M + H] 172.2.
17.1 g With hydrogen; In tetrahydrofuran; methanol; Methyl 5-methyl-4-nitrothiophene-2-carboxylate (24.3 g) was dissolved in a mixture of THF (100 mL) and methanol (100 mL) and then to this solution was added wet Raney Ni. The solution was degassed, refilled with hydrogen, and stirred over an atmosphere of hydrogen overnight. The mixture was filtered through a pad of Celite and concentrated to afford the title product (17.1 g), which was used directly in the next synthetic step. LC (method A): = 0.55 min. LC/MS (EI) mlz: [M + H]+ 172.2.

  • 2
  • [ 56921-01-8 ]
  • [ 7440-02-0 ]
  • [ 501082-56-0 ]
YieldReaction ConditionsOperation in experiment
In methanol; Step 1 5-Methyl-4-amino-thiophene-2-carboxylic Acid Methyl Ester Sponge nickel (1.0 g water wet) was added to a solution of <strong>[56921-01-8]5-methyl-4-nitro-thiophene-2-carboxylic acid methyl ester</strong> (1.79 g, 8.9 mmol) in methanol (50 mL), and the mixture was hydrogenated at room temperature under a hydrogen atmosphere at a starting pressure of 50 psi. After a reaction time of 25 hours, the pressure was released and the mixture filtered. The slurry was rinsed with methanol, and the filtrate was stripped of solvent under reduced pressure to afford 1.5 g of 5-methyl-4-amino-thiophene-2-carboxylic acid methyl ester. A sample was dissolved in ethyl acetate and filtered through a short column of silica gel. Evaporation of the effluent under reduced pressure gave product with a mp 90-91 C.
 

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