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Chemical Structure| 287193-06-0 Chemical Structure| 287193-06-0

Structure of 287193-06-0

Chemical Structure| 287193-06-0

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Product Details of [ 287193-06-0 ]

CAS No. :287193-06-0
Formula : C8H10O4
M.W : 170.16
SMILES Code : CCOC(=O)C1CC(=O)C=CO1
MDL No. :MFCD20922880

Safety of [ 287193-06-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319
Precautionary Statements:P264-P280-P302+P352-P305+P351+P338-P332+P313-P337+P313-P362

Application In Synthesis of [ 287193-06-0 ]

* 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 [ 287193-06-0 ]

[ 287193-06-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 287193-06-0 ]
  • [ 287193-07-1 ]
YieldReaction ConditionsOperation in experiment
80% With palladium 10% on activated carbon; hydrogen; In ethyl acetate; at 20℃; for 12h;Inert atmosphere; Into a 100-mL round-bottom flask containing a solution of 258.2 (2.0 g, 11.75 mmol, 1.00 equiv) in ethyl acetate (50 mL) was added palladium on activated carbon (10%, 200 mg) under nitrogen at room temperature. Then (g) was introduced in and degassed three times. The resulting solution was stirred for 12 h at ambient temperature. The solids were filtered out by filtration and washed with EtOAc (3 x). The filtrate was concentrated under reduced pressure and the residue was purified by silica gel column with EtOAc/PE (1:20) to give the desired 258.3 (1.62 g, 80%) as a light yellow oil.
60% With hydrogen;palladium 10% on activated carbon; In ethyl acetate; under 1551.49 Torr; for 1.5h; To a solution of the above of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (1.0 g, 5.9 mmol) in ethyl acetate (12 ml) was added 10 % palladium on activated carbon (0.15 g). The reaction was shaken on a Parr hydrogenator under a hydrogen atmosphere (30 psi) for 1.5 hour. The mixture was filtered through celite and concentrated invacuo. The residue was purified by silica gel chromatography using diethyl ether as eluent. Pure fractions were collected and the solvent evaporated invacuo which affording 0.6 g (60 %) of 4-oxo-tetrahydro-2H-pyran-2-carboxylic acid ethyl as an oil.1H-NMR (300 MHz, CDCl3) delta 4.41-4.35 (m, 1H), 4.26 (q, 2H, J = 7 Hz), 3.81-3.70 (m, 1H), 2.73-2.58 (m, 3H), 2.44-2.36 (m, 1H), 1.29 (t, 3H, J = 7 Hz).
60% With hydrogen;palladium 10% on activated carbon; In ethyl acetate; under 1551.49 Torr; for 1.5h; To a solution of the above of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (1.0 g, 5.9 mmol) in ethyl acetate (12 ml) was added 10% palladium on activated carbon (0.15 g). The reaction was shaken on a Parr hydrogenator under a hydrogen atmosphere (30 psi) for 1.5 hour. The mixture was filtered through celite and concentrated in vacuo. The residue was purified by silica gel chromatography using diethyl ether as eluent. Pure fractions were collected and the solvent evaporated in vacuo which affording 0.6 g (60%) of 4-oxo-tetrahydro-2H-pyran-2-carboxylic acid ethyl as an oil.1H-NMR (300 MHz, CDCl3) delta 4.41-4.35 (m, 1H), 4.26 (q, 2H, J=7 Hz), 3.81-3.70 (m, 1H), 2.73-2.58 (m, 3H), 2.44-2.36 (m, 1H), 1.29 (t, 3H, J=7 Hz).
60% With hydrogen;palladium 10% on activated carbon; In ethyl acetate; under 1551.49 Torr; for 1.5h; Example 30 2-(Oxalyl-amino)-5-phenylcarbamoyl-4,7-dihydro-5H-thieno[2,3-c]pyran-3 carboxylic acid; A solution of glyoxylic acid ethyl ester, polymer form (2.02 g, 8.9 mmol) and (3-methoxy-1-methylene-allyloxy)-trimethyl-silane (1.9 ml, 8.9 mmol, Danishefsky's diene) in benzene (12 ml) was placed under nitrogen. Zinc chloride (0.5N in tetrahydrofuran, 8.9 ml, 4.45 mmol) was added and the reaction stirred at ambient temperature for 72 h. The mixture was concentrated in vacuo, diluted with ethyl acetate (100 ml) and washed with 1 N hydrochloric acid (20 ml), saturated sodium bicarbonate (20 ml), and brine (20 ml). The organic layer was dried (Na2SO4), filtered, and the solvent evaporated in vacuo. The residue was purified by silica gel chromatography using a mixture of ethyl acetate/hexane (1:2) as eluant. Pure fractions were collected and the solvent evaporated in vacuo which afforded 1.2 g (75%) of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester as an oil.1H NMR (400 MHz, CDCl3) delta 7.40 (d, J=6, 1H), 5.48 (d, J=6, 1H), 5.01 (t, J=8, 1H), 4.28 (q, J=7, 2H), 2.85 (d, J=8, 2H), 1.29 (t, J=7, 3H).To a solution of the above of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (1.0 g, 5.9 mmol) in ethyl acetate (12 ml) was added 10% palladium on activated carbon (0.15 g). The reaction was shaken on a Parr hydrogenator under a hydrogen atmosphere (30 psi) for 1.5 h. The mixture was filtered through celite and concentrated in vacuo. The residue was purified by silica gel chromatography sing diethyl ether as eluant. Pure fractions were collected and the solvent evaporated in vacuo which affording 0.6 g (60%) of 4-oxo-tetrahydro-2H-pyran-2-carboxylic acid ethyl as an oil.1H NMR (300 MHz, CDCl3) delta 4.41-4.35 (m, 1H), 4.26 (q, J=7, 2H), 3.81-3.70 (m, 1H), 2.73-2.58 (m, 3H), 2.44-2.36 (m, 1H), 1.29 (t, J=7, 3H).To a solution of 4-oxo-tetrahydro-2H-pyran-2-carboxylic acid ethyl (0.6 g, 3.5 mmol) in absolute ethanol (6 ml) was added sulfur (0.12 g, 3.85 mmol) and tert-butyl cyanoacetate (0.64 g, 4.55 mmol). The solution was stirred under nitrogen in a 50 C. oil bath and morpholin (0.61 ml, 7.0 mmol) was added. The reaction was stirred for 18 h. and then cooled to ambient temperature and excess sulfur removed by filtration. The filtrate was concentrated in vacuo and reconstituted in ethyl acetate (50 ml). The organic phase was washed with brine (2×10 ml), dried (Na2SO4), filtered, and the solvent evaporated in vacuo. The residue was purified by silica gel chromatography using a gradient of ethyl acetate/hexane (20 to 25% gradient) as eluant. Pure fraction of the two isomers were collected and the solvent evaporated in vacuo which afforded 0.47 g of 2-amino-4,7-dihydro-5H-thieno[2,3-c]pyran-3,5-dicarboxylic acid 3-tert-butyl ester 5-ethyl ester (A) and 0.3 g of 2-amino-4,7-dihydro-5H-thieno[2,3-c]pyran-3,7-dicarboxylic acid 3-tert-butyl ester 7-ethyl ester (B) in 62% combined yield.(A)1H NMR (300 MHz, CDCl3) delta 5.96 (bs, 2H), 4.77-4.61 (m, 2H), 4.32-4.18 (m, 3H), 3.19-3.12 (m, 1H), 2.90-2.80 (m, 1H), 1.52 (s, 9H), 1.29 (t, J=7, 3H).APCI-MS: [M+H]+=272.4 (loss of t-butyl)(B)1H NMR (300 MHz, CDCl3) delta5.10 (s, 1H), 4.28-4.13 (m, 3H), 3.98-3.91 (m, 1H), 2.82-2.76 (m, 2H), 1.51 (s, 9H), 1.31 (t, J=7, 3H).APCI-MS: [M+H]+=272.4 (loss of t-butyl)The above 2-amino-4,7-dihydro-5H-thieno[2,3-c]pyran-3,5-dicarboxylic acid 3-tert-butyl ester 5-ethyl ester (275 mg, 0.84 mmol) was dissolved in a mixture of ethanol (4 ml) and tetrahydrofuran (1 ml). Sodium hydroxide (1N, 1.6 ml, 1.68 mmol) was added and the reaction stirred at ambient temperature for 5 h. after which TLC analysis indicated that the reaction was complete. The reaction was monitored with a pH meter and neutralized with 1N hydrochloric acid until pH=6.9. The solution was concentrated in vacuo to give 2-amino-4+/-7-dihydro-5H-thieno[2,3-c]pyran-3,5-dicarboxylic acid 3-tert-butyl ester as a solid. Sodium chloride remained as an impurity.1H NMR (300 MHz, CD3OD) delta 4.67-4.54 (m, 2H), 4.00-3.95 (m, 1H), 3.20-3.12 (m, 1H), 2.74-2.63 (m, 1H), 1.54 (s, 9H).APCI-MS: [M+H]+=300.0To a solution of the above 2-amino-4,7-dihydro-5H-thieno[2,3-c]pyran-3,5-dicarboxylic acid 3-tert-butyl ester (94 mg, 0.31 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (72 mg, 0.37 mmol) in distilled dichloromethane (4 ml) under nitrogen was added aniline (32 mul, 0.34 mmol) followed by 2,6-lutidine (0.11 ml, 0.93 mmol). The reaction was stirred for 72 h., concentrated in vacuo and reconstituted in ethyl acetate (30 ml). The organic layer was washed with 1% hydrochloric acid (10 ml), saturated sodium bicarbonate (10 ml), brine (10 ml), dried (Na2SO4), filtered, and the solvent evaporated in vacuo to give 51 mg (45%) of 2-amino-5-phenylcarbamoyl-4,7-dihydro-5H-thieno[2,3-c]pyran-3-carboxylic acid tert-butyl ester as a solid.1H NMR (400 MHz, CDCl3) delta 8.40 (s, 1H), 7.60 (d, 1H, J=7), 7.49 (d, 1H, =8), 7.34 (t, 1H, J=8), 7.32 (t, 1H, J=8), 7.13 (t, 1H, J=7)...
33% With palladium on activated charcoal; hydrogen; In ethyl acetate; under 760.051 Torr; for 4h; 1002881 Step B: A mixture of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (8.0 g, 46 mmol) and Pd/C (10%, 0.20 g) in ethyl acetate (70 mL) was stirred under hydrogen (1 atm) for 4 hours. The mixture was filtered through a pad of Celite. The filtrate was concentrated, and the residue was purified by silica gel column using 30% EtOAc in petroleum ether to give 4-oxo-tetrahydro-pyran-2-carboxylic acid ethyl ester (2.62 g, 33% yield) as an oil. ?H NMR (500 MHz, CDC13) 6 4.40 (m, 1H), 4.23-4.3 1 (m, 3H), 3.79 (m, 1H), 2.6 1-2.74 (m, 3H), 2.40 (d, J = 15.0 Hz, 1H), 1.31 (t, J = 7.5 Hz, 3H).
2.62 g (33%) palladium-carbon; In hydrogen; ethyl acetate; 4-Oxo-tetrahydro-pyran-2-carboxylic acid ethyl ester: A mixture of 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (8.0 g, 46.0 mmol) and Pd/C (10%, 0.20 g) in EtOAc (70 mL) was shaken in a Parr bottle with hydrogen at 50 psi overnight and filtered through a pad of Celite. The filtrate was concentrated and the residue was distilled to give 2.62 g (33%) of yellowish oil: 1H NMR (CDCl3) delta 1.29 (t, 3H), 2.40 (d, 1H), 2.58-2.75 (m 3H), 3.79 (tt, 1H), 4.23 (q, 2H), 4.28 (m 1H), 4.40 (m, 1H).

 

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