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Chemical Structure| 40896-96-6 Chemical Structure| 40896-96-6

Structure of 40896-96-6

Chemical Structure| 40896-96-6

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Product Details of [ 40896-96-6 ]

CAS No. :40896-96-6
Formula : C8H12O2
M.W : 140.18
SMILES Code : O=C(C1CC(C1)=C)OCC
MDL No. :MFCD18382027
InChI Key :DUCWJRFQAGUNFE-UHFFFAOYSA-N
Pubchem ID :18706839

Safety of [ 40896-96-6 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H225-H315-H319-H335
Precautionary Statements:P210-P261-P280-P301+P312-P302+P352-P305+P351+P338
Class:3
UN#:3272
Packing Group:

Application In Synthesis of [ 40896-96-6 ]

* 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 [ 40896-96-6 ]

[ 40896-96-6 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 15760-36-8 ]
  • [ 40896-96-6 ]
YieldReaction ConditionsOperation in experiment
With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; for 16h; Iodoethane (7.5 mL, 93.0 mol) was added at rt to a mixture of <strong>[15760-36-8]3-methylenecyclobutanecarboxylic acid</strong> (10.0 g, 80.0 mmol) and cesium carbonate (56.0 g, 170.0 mmol) in anhydrous N,N-dimethylformamide (500.00 mL) under an atmosphere of nitrogen. The reaction was stirred for 16 hr then partitioned between diethyl ether (1 L) and brine (1 L). The aqueous layer was extracted with diethyl ether (3×500 mL) and the combined organic phases washed with water (2×1 L), dried over sodium sulfate, filtered and concentrated in vacuo to yield desired product 1H NMR (400 MHz, CDCl3) δ ppm 1.26 (t, 3H), 2.71-3.27 (m, 5H), 4.15 (q, J=7.07 Hz, 2H) and 4.53-4.96 (m, 2H).
  • 2
  • [ 15760-36-8 ]
  • [ 75-03-6 ]
  • [ 40896-96-6 ]
YieldReaction ConditionsOperation in experiment
97% With caesium carbonate; In N,N-dimethyl-formamide; at 20℃;Inert atmosphere; Example 151 A ethyl 3 -methylenecyclobutanecarboxylate A mixture of <strong>[15760-36-8]3-methylenecyclobutanecarboxylic acid</strong> (CAS 15760-36-8) (2.06 g, 18.37 mmol), ethyl iodide (1.782 mL, 22.05 mmol) and Cs2C03 (13.17 g, 40.4 mmol) in N,N- dimethylformamide (100 mL) under N2 was stirred at room temperature overnight. The mixture was poured slowly into a stirred 0 C mixture of 0.2 M HCl (500 mL) and methyl tert-butyl ether (1000 mL). The layers were separated and the methyl tert-butyl ether layer was washed with water (500 mL x 2), washed with brine, dried (MgS04), filtered, and concentrated to provide the title compound (2.5 g, 17.83 mmol, 97 % yield). 1H NMR (500 MHz, CDC13) δ 4.83 (p, J= 2.3 Hz, 2H), 4.19 (q, J= 7.1 Hz, 2H), 3.18 - 3. 11 (m, 1H), 3.07 - 3.00 (m, 2H), 2.97 - 2.89 (m, 2H), 1.30 (t, J = 7.1 Hz, 3H).
85% With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; for 15h; To a solution of 3 -methylenecyclobutane-1 -carboxylic acid [15760-36-8] (10 g, 89.18 mmol) and iodoethane [75-03-6] (14.34 mL, 178.37 mmol) in DMF dry (150 mL), Cs2C03 [534-17-8] (72.65 g, 222.96 mmol) was added and the mixture was stirred at room temperature for 15 hr. The mixture was diluted with ethylacetate and washed with brine (5X). The organic layer was dried (MgSO4), filtered and concentrated to yield 3- methylenecyclobutane-l-carboxylate (10600 mg, yield 85%) as a colourless oil. 1H NMR (300 MHz, CDC13) d 4.84 - 4.74 (m, 2H), 4.14 (q, J = 7.1 Hz, 2H), 3.20 - 2.81 (m, 5H), 1.25 (t, J = 7.1 Hz, 3H).
With caesium carbonate; In N,N-dimethyl-formamide; for 16h; Iodoethane (7.5 mL, 93.0 mol) was added at rt to a mixture of <strong>[15760-36-8]3-methylenecyclobutanecarboxylic acid</strong> (10.0 g, 80.0 mmol) and cesium carbonate (56.0 g, 170.0 mmol) in anhydrous N,N-dimethylformamide (500.00 mL) under an atmosphere of nitrogen. The reaction was stirred for 16 hr then partitioned between diethyl ether (1 L) and brine (1 L). The aqueous layer was extracted with diethyl ether (3×500 mL) and the combined organic phases washed with water (2×1L), dried over sodium sulfate, filtered and concentrated in vacuo to yield desired product 1H NMR (400 MHz, CDCl3) δ ppm 1.26 (t, 3H), 2.71-3.27 (m, 5H), 4.15 (q, J=7.07 Hz, 2H) and 4.53-4.96 (m, 2H).
13.6 g With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 8h; Preparation of reagent R-1 1 a: ethyl 3-methylenecvclobutanecarboxylate To a solution of commercially available 3-methylenecyclobutanecarbonitrile (10.7 g, 1 15 mmol) in EtOH (70 mL) was added KOH (25.2 g, 450 mmol), then the mixture was stirred at reflux overnight. The resulting mixture was stirred at reflux overnight until TLC showed the starting material was consumed completely, the solvent was evaporated and water was added. 1 N HCI was added to bring pH to ~3 and extracted with EtOAc, the organic layer was washed with brine, dried over anhydrous Na2SO4, concentrated to give the crude product (12.3 g,~95%). The crude product (12.3 g, 1 10 mmol) was dissolved in DMF (120 mL). Then Etl (21 .5 g, 138 mmol) and K2CO3 (31 .7 g, 230 mmol) were added to this solution. The mixture was stirred at r.t. for 8 h. Then water was added and extracted with EtOAc, the organic layer was washed with brine, dried over anhydrous Na2SO4, concentrated to give a crude which was purified by column to give the reagent R-1 1 a (13.6 g, 88% yield) as a pale yellow oil. GC-MS (M): 140 calc. for C8H12O2: 140.08.
With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; for 5h; To a solution of R-06b-2 (9.3 g, 83 mmol) in DMF (100 mL) was added Cs2C03(32.4 g, 99 mmol) and iodoethane (15.5 g, 99 mmol) and the mixture was stirred at 20 C for 5 hours. Then, the mixture was filtered and the filtrated was diluted with water and extracted with MTBE. The combined organic layers were washed with brine, dried over anhydrous Na2S04, filtered and concentrated under reduced pressure to give R-06b-3 (9.5 g, 82%) as yellow oilsolid. This compound was used in the next step without further characterization.
4.1 g In N,N-dimethyl-formamide; at 20℃; for 16h;Inert atmosphere; Add <strong>[15760-36-8]3-methylenecyclobutane-1-carboxylic acid</strong> (4g, 35.7mmol) to N,N-dimethylformamide (60mL) at room temperature, and under nitrogen protection, add ethyl iodide (4g, 35.7mmol) at room temperature. 6.6g, 42.8mmol), reacted at room temperature for 16 hours.After the reaction was completed, the reaction solution was slowly poured into 1mol/L hydrochloric acid (200mL) at 0C, extracted twice with methyl tert-butyl ether (200mL), and the organic phase was washed twice with water (50mL) and saturated chlorinated The sodium solution (100 mL) was washed 3 times, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain ethyl 3-methylenecyclobutane-1-carboxylate (111-2) (4.1 g).

 

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