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Chemical Structure| 130312-00-4 Chemical Structure| 130312-00-4
Chemical Structure| 130312-00-4

Ethyl 2-(dihydro-2H-pyran-4(3H)-ylidene)acetate

CAS No.: 130312-00-4

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Cat. No.: A737194 Purity: 98%

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Product Details of [ 130312-00-4 ]

CAS No. :130312-00-4
Formula : C9H14O3
M.W : 170.21
SMILES Code : O=C(OCC)/C=C1CCOCC/1
MDL No. :MFCD09475810
InChI Key :HMRYLZJIPRVVCW-UHFFFAOYSA-N
Pubchem ID :11105795

Safety of [ 130312-00-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338

Application In Synthesis of [ 130312-00-4 ]

* 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 [ 130312-00-4 ]

[ 130312-00-4 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 130312-00-4 ]
  • [ 103260-44-2 ]
YieldReaction ConditionsOperation in experiment
100% Pd/NH4COOH; at 80℃; Ethyltetrahydro-4H-pyran-4-ylacetate was prepared from ethyltetrahydro-4H-pyran-4-ylideneacetate (16.0 g, 94 mmol) and Pd/ NH4COOH at 80 C. Colorless oil, Yield: 16.3 g, quantitaive), MS: 173.2 (M+H)+
99% With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃; under 760.051 Torr; b) To a solution of 425 mg (2.5 mmol) of ethyl 2-(dihydro-2H-pyran-4(3H)- ylidene)acetate in 15 mL of MeOH, 133 mg of Pd on carbon 10% was added. Hydrogen atmosphere was set (1 atm, with a balloon) and the reaction was stirred at room temperature overnight. It was filtered through a pad of celite washing with abundant EtAcO. After removing the solvent the desired compound ethyl 2- (tetrahydro-2H-pyran-4-yl)acetate was obtained as a colorless oil (99%).
98.5% palladium-carbon; In ethanol; Ethyl 2-(4-oxanyl)acetate To a solution of ethyl 2-(4-oxanylidene)acetate (22.0 g, 139 mmol) in ethanol (50 mL) was added 10% Pd/C (2.2 g) and the mixture subjected to hydrogenation overnight on a Parr apparatus (50 psi). The catalyst was removed by filtration through Celite, which was washed with ethanol (25 mL). Removal of solvent from the combined filtrates by rotary evaporation gave the desired product as a colorless oil (22.0 g, 98.5%).
94% With palladium on activated charcoal; hydrogen; In methanol; at 16 - 19℃; under 1551.49 Torr; for 18h; A mixture of ethyl 2-(dihydro-2H-pyran-4(3H)-ylidene) acetate (21 g, 123 mmol) and dry Pd/C (2.5 g) in methanol (300 mE) was stirred at 16-19 C. for 18 h under H2 (30 psi). TEC (petroleum ether:ethyl acetate=3:1) showed no starting material remaining. The mixture was filtered and the filtrate was concentrated under reduced pressure to give crude ethyl5 2-(tetrahydro-2H-pyran-4-yl)acetate (20 g, 94%) as an oil, which was used for the next step directly without further purification. ?H NMR (CDC13, 400 MHz): oe 4.11-4.15 (q, J=7.2 Hz, 2H), 3.93-3.95 (d, J=10.8 Hz, 2H), 3.37-3.43 (t, J=11.6 Hz, 2H), 2.23-2.25 (d, J=6.8 Hz, 2H), 1.99-2.03 (m,10 1H), 1.62-1.65 (m, 2H), 1.32-1.36 (m, 2H), 1.24-1.27 (t, J=7.2 Hz, 3H).
84% With sodium tetrahydroborate; nickel dichloride; In methanol; at 0℃; for 0.5h; To a solution of ethyl 2-(tetrahydro-4H-pyran-4-ylidene)acetate (0.4 g, 2.33 mmol) in methanol (5 ml) was added NaBH4 (0.198 g, 5.29 mmol) portionwise at 0 C. After 30 mm of stirring at 0 C NiC12 (0.12 g, 0.505 mmol) was added slowly. After stirring for 45mm the reaction solvent was evaporated under reduced pressure and diluted with water (10 ml) and the product was extracted with ethyl acetate (3x 10 ml). The combined organic layer was concentrated under reduced pressure to afford the title compound (84%). ?H NMR (400MHz, CDC13) & 4.18-4.13 (q, 1=7.2Hz, 2H), 3.99-3.95 (m, 2H), 3.46-3.40 (m, 2H), 2.27-2.25 (m, 2H), 2.10-1.98 (m, 1H), 1.64 (s, 2H), 1.41-1.23 (m, 5H).
78% With palladium 10% on activated carbon; ammonium formate; In methanol; at 70℃; for 15h; To a mixture composed of ethyl 2-(2H-pyran-4(3H,5H,6H)-ylidene)acetate (10 g, 58.75 mmol) and ammonium formate (37 g, 587.54 mmol) in methanol (150 ml) was added 10% Pd-carbon (1.0 g) at room temperature, and the mixture was stirred at 70 C for 15 hr. The reaction mixture was allowed to cool to room temperature, and the catalyst was collected by filtration through Celite pad and was washed with methanol. The filtrate was concentrated under reduced pressure, and the residue was chromatographed on silica gel column (hexane:ethyl acetate = 94:6) to give the title compound as an oil (7.9 g, yield 78%). 1H-NMR (400 MHz, CDCl3): delta (ppm) 4.13 (q, J = 7.2 Hz, 2H ), 3.97-3.93 (m, 2H), 3.44-3.38 (m, 2H), 2.24 (d, J = 7.2 H z, 2H), 2.08-1.92 (m, 1H) 1.66-1.62 (m, 2H), 1.40-1.29 (m, 2H), 1.26 (t, J = 7.2 Hz, 3H); MS (ESI): m/z 172 (M+).
With hydrogen;palladium 10% on activated carbon; In methanol; at 25℃; under 1551.49 Torr; for 20h; A mixture of (tetrahydro-pyran-4-ylidene)-acetic acid ethyl ester (27 g, 159 mmol) and 10% palladium on activated carbon (3 g) in methanol (300 mL) was stirred at 25 C. under 30 psi of hydrogen for 20 h. The catalyst was filtered off, washed with ethyl acetate and concentrated in vacuo to afford (tetrahydro-pyran-4-yl)-acetic acid ethyl ester (25 g, 91%) as a colorless oil which was used in the next step without purification.
With palladium on activated charcoal; hydrogen; In methanol; at 16 - 19℃; under 1551.49 Torr; for 18h; [00105] A mixture of ethyl 2-(dihydro-2H-pyran-4(3H)-ylidene)acetate (21 g, 123 mmol) and dry Pd/C (2.5 g) in methanol (300 mL) was stirred at 16-19 C for 18 h under H2 (30 psi). TLC (petroleum ether: ethyl acetate = 3: 1) showed no starting material remaining. The mixture was filtered and the filtrate was concentrated under reduced pressure to give crude ethyl 2-(tetrahydro-2H-pyran-4-yl)acetate (20 g, 94%) as an oil, which was used for the next step directly without further purification. 1H NMR (CDC13, 400 MHz): delta 4.11-4.15 (q, J = 7.2 Hz, 2H), 3.93-3.95 (d, J = 10.8 Hz, 2H), 3.37-3.43 (t, J = 11.6 Hz, 2H), 2.23-2.25 (d, J = 6.8 Hz, 2H), 1.99-2.03 (m, 1H), 1.62-1.65 (m, 2H), 1.32-1.36 (m, 2H), 1.24-1.27 (t, J = 7.2 Hz, 3H).

  • 2
  • ethyl 3,6-dihydro-2H-pyran-4-ylacetate [ No CAS ]
  • [ 130312-00-4 ]
  • [ 103260-44-2 ]
YieldReaction ConditionsOperation in experiment
With hydrogen;palladium 10% on activated carbon; In ethyl acetate; for 18h; A mixture of 15.0 and 16.0 (3 g, 17.6 mmol) from Preparative Example 10 was dissolved in 20 mL of ethyl acetate containing 1.0 g of 10% paladium on carbon. This mixture was stirred for 18 hours under an atmosphere of hydrogen. The catalyst was filtered and the filtrate was concentrated under vacuum giving 3.04 g of the title product as a colorless oil
  • 3
  • [ 130312-00-4 ]
  • [ 909406-73-1 ]
 

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Technical Information

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