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Chemical Structure| 89941-55-9 Chemical Structure| 89941-55-9

Structure of 89941-55-9

Chemical Structure| 89941-55-9

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Product Details of [ 89941-55-9 ]

CAS No. :89941-55-9
Formula : C7H12O3
M.W : 144.17
SMILES Code : O=C(C1CC(CO)C1)OC
MDL No. :MFCD13659363

Safety of [ 89941-55-9 ]

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 [ 89941-55-9 ]

* 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 [ 89941-55-9 ]

[ 89941-55-9 ] Synthesis Path-Downstream   1~2

  • 2
  • [ 15963-40-3 ]
  • [ 89941-55-9 ]
YieldReaction ConditionsOperation in experiment
95% A dry three-neck flask was charged with methyl 3- methylenecyclobutanecarboxylate 3 (24.46g, 0.21 mol) and dry THF (130ml) and cooled to -10C, then borane-THF complex (70.0mL) was added via a syringe dropwise. The resulting mixture was stirred for 4h at r.t and was cooled to -20C~- 10C; methanol was added, stirred for 15min. Sodium hydroxide (3M 30ml_) and hydrogen peroxide (34. Og, 0.21 Omol) were added in sequence. The mixture was stirred for 2h and saturated sodium sulfite solution (100ml_) was added. The reaction mixture was diluted with water, then extracted with ethyl acetate, washed with water and brine, dried over sodium sulfate, filtered, removed the solvent and the residue was purified with silica gel chromatography. (28.73g, 95%)
87% Methyl-3-methylene cyclobutane carboxylic acid(2.00g, 15.8mmol) was dissolved in tetrahydrofuran (30 mL), andWas added dropwise at -10C borane dimethyl sulfide (3.61g, 47.5mmol), then -10C for 3 hours, was added 3N aqueous sodium hydroxide (10mL) and hydrogen peroxide (5mL), reaction was continued for 1 hour, the reaction solution was added a saturated aqueous sodium thiosulfate solution (30 mL) to quench the reaction, and extracted with dichloromethane (10mLx3), dried over anhydrous Sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give methyl 3-(hydroxymethyl)cyclobutanoate (2.00 g,Yellow oil). Yield: 87%.
68% 3.1.57b (24 g, 190.4 mmol, 1.0 equiv) was dissolved in THE and cooled to -15 C. BH3.Me2S (14.4 g, 190.4 mmol, 1.0 equiv) was added drop wise and the reaction mixture was stirred at room temperature for 4 hours. Cooled the reaction mixture at -15 C, NaOH (3M) (25 mL), H202 (50%) (12.9 g, 190.4 mmol, 1.0 equiv) were added and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was quenched with sodium bisulphate and extracted with EtOAc. The organic layer was washed with brine,dried over sodium sulfate and concentrated to afford a crude residue. The crude residue was purified by silica gel column chromatography (70 % EtOAc in Hexane) to afford product 3.1.57c (18.7 g, 68 % yield). 1H NMR (400 MHz, DMSO) 64.54 (d, J = 29.8 Hz, 1H), 3.62-3.55 (m, 3H), 3.41 (d, J = 6.5 Hz, 1H), 3.30 (d, J = 6.0 Hz, 1H), 3.13-2.95 (m, 1H), 2.37-2.27 (m, 1H), 2.15 (ddt, J= 8.7, 7.8, 6.2 Hz, 2H), 1.98- 1.84(m, 2H).
58% a solution of borane-THF (56 mL, 0.80 eq.) was added dropwise over 30 mm to a cold (-10 C) solution of <strong>[15963-40-3]methyl 3-methylidenecyclobutane-1-carboxylate</strong> (10 g, 79.27 mmol, 1.00 eq.) in THF (100 mL). The resulting solution was stirred for 3 hours at 25 C. The mixture was cooled to -10 Cand methanol (20 mL) was added slowly and the mixture was stirred for 30 mm at 25 C. The reaction mixture was cooled to -10 C and H202 (9 g, 79.41 mmol, 1.00 eq., 30%) was added dropwise (5 mm) followed by dropwise addition of sodium hydroxide aqueous (12.5 mL) at -10C. The resulting solution was stirred for 3 hours at 25 C. The reaction was then quenched by the addition of Na2SO3 aqueous. The resulting solution was diluted with water (300 mL) andthen extracted with ethyl acetate (2x300 mL) and the organic layers combined. The resulting mixture was washed with brine (2x300 mL), dried over anhydrous sodium sulfate and concentrated under vacuum to give methyl 3 -(hydroxymethyl)cyclobutane- 1 -carboxylate as colorless oil (6.6 g, 58%).
54% To a solution of <strong>[15963-40-3]methyl <strong>[15963-40-3]3-methylenecyclobutanecarboxylate</strong></strong> (5.3 g, 42.4 mmol, 1.0 eq) in THF (30 mL) was added BH3 (12.6 mL, 12.6 mmol, 0.3 eq, 1 M) dropwise at 0 C. Then the reaction mixture was warmed to ft and stirred for 4 h. MeOH (15 mL) was added and the mixture was stirred for 30 mm at 0 C. NaOH (4.2 mL, 3M) and H202 (1.4 g, 42.4 mmol, 1.0 eq) wereadded and stirred at 0 C for 1 h. The mixture was quenched with water (30 mL) and extracted with Et20 (60 mL X 2). The combined organic phases were dried over Na2SO4 After filtration and concentration, 3.3 g of methyl 3-(hydroxymethyl)cyclobutanecarboxylate as yellow oil was obtained. Y: 54%. ESI-MS (M+H): 145.0. ?H NMR (400 MHz, CD3OD) (5: 3.69 (s, 1.3H), 3.67 (s, 1.7H), 3.59 (s, 0.4H), 3.58 (s, 0.5H), 3.50 (s, 0.4H), 3.48 (s, 0.5H), 3.12-3.03 (m, 1H), 2.48-2.38 (m, 1H), 2.35-2.22 (m, 2H), 2.08-1.94 (m, 2H).
2.92% A dry three-neck flask was charged with <strong>[15963-40-3]methyl <strong>[15963-40-3]3-methylenecyclobutanecarboxylate</strong></strong> (6 g, 47.6 mmol) and dry THF (20 ml) and cooled to -10 C. BH3.THF (12.26 g, 143 mmol) was then added via a syringe dropwise. The resulting mixture was stirred for 4h at rt and was cooled to -20 C - 10C. Methanol was then added and the mixture was stirred for 15min. Sodium hydroxide (3M; 30 ml) and H2O2 (7.29 ml_, 238 mmol) were added in sequence. The mixture was stirred for 2h and a saturated sodium sulfite solution (100 ml) was added. The reaction mixture was diluted with water, then extracted with ethyl acetate, washed with water and brine, dried over sodium sulfate, filtered, and the residue was purified by flash chromatography eluting with (petroleum ether/EtOAc = 3/1 ) to afford methyl 3- (hydroxymethyl)cyclobutanecarboxylate (250 mg, 1 .387 mmol, 2.92 % yield) as a yellow oil.
6.6 g Step 1C: methyl 3-(hydroxymethyl)cyclobutane-l-carboxylate: a solution of borane-THF (56 mL, 0.80 eq.) was added dropwise over 30 min to a cold (-10 C) solution of methyl 3-methylidenecyclobutane-l -carboxylate (10 g, 79.27 mmol, 1.00 eq.) in THF (100 mL). The resulting solution was stirred for 3 hours at 25 C. The mixture was cooled to -10 C and methanol (20 mL) was added slowly and the mixture was stirred for 30 min at 25 C. The reaction mixture was cooled to -10 C and H202 (9 g, 79.41 mmol, 1.00 eq., 30%) was added dropwise (5 min) followed by dropwise addition of sodium hydroxide aqueous (12.5 mL) at -10 C. The resulting solution was stirred for 3 hours at 25 C. The reaction was then quenched by the addition of Na2S03 aqueous. The resulting solution was diluted with water (300 mL) and then extracted with ethyl acetate (2x300 mL) and the organic layers combined. The resulting mixture was washed with brine (2x300 mL), dried over anhydrous sodium sulfate and concentrated under vacuum to give methyl 3-(hydroxymethyl)cyclobutane- l -carboxylate as colorless oil (6.6 g, 58%).
6.6 g a solution of borane-THF (56 mL, 0.80 eq.) was added dropwise over 30 min to a cold (-10 C) solution of methyl 3-methylidenecyclobutane-l-carboxylate (10 g, 79.27 mmol, 1.00 eq.) in THF (100 mL). The resulting solution was stirred for 3 hours at 25 C. The mixture was cooled to -10 C and methanol (20 mL) was added slowly and the mixture was stirred for 30 min at 25 C. The reaction mixture was cooled to -10 C and H2O2 (9 g, 79.41 mmol, 1.00 eq., 30%) was added dropwise (5 min) followed by dropwise addition of sodium hydroxide aqueous (12.5 mL) at -10 C. The resulting solution was stirred for 3 hours at 25 C. The reaction was then quenched by the addition of Na2SC>3 aqueous. The resulting solution was diluted with water (300 mL) and then extracted with ethyl acetate (2x300 mL) and the organic layers combined. The resulting mixture was washed with brine (2x300 mL), dried over anhydrous sodium sulfate and concentrated under vacuum to give methyl 3-(hydroxymethyl)cyclobutane-l-carboxylate as colorless oil ( 6.6 g, 58%).
6.6 g a solution of borane-THF (56 mL, 0.80 eq.) was added dropwise over 30 min to a cold (-10 C) solution of methyl 3-methylidenecyclobutane-l -carboxylate (10 g, 79.27 mmol, 1.00 eq.) in THF (100 mL). The resulting solution was stirred for 3 hours at 25 C. The mixture was cooled to -10 C and methanol (20 mL) was added slowly and the mixture was stirred for 30 min at 25 C. The reaction mixture was cooled to -10 C and H2O2 (9 g, 79.41 mmol, 1.00 eq., 30%) was added dropwise (5 min) followed by dropwise addition of sodium hydroxide aqueous (12.5 mL) at -10 C. The resulting solution was stirred for 3 hours at 25 C. The reaction was then quenched by the addition of Na2SC>3 aqueous. The resulting solution was diluted with water (300 mL) and then extracted with ethyl acetate (2x300 mL) and the organic layers combined. The resulting mixture was washed with brine (2x300 mL), dried over anhydrous sodium sulfate and concentrated under vacuum to give methyl 3-(hydroxymethyl)cyclobutane-l -carboxylate as colorless oil ( 6.6 g, 58%).

 

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