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Chemical Structure| 1138480-98-4 Chemical Structure| 1138480-98-4

Structure of 1138480-98-4

Chemical Structure| 1138480-98-4

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Product Details of [ 1138480-98-4 ]

CAS No. :1138480-98-4
Formula : C9H12O3
M.W : 168.19
SMILES Code : COC(=O)C1CC2(C1)CC(=O)C2
MDL No. :MFCD20922770
InChI Key :KPVYGLFZWUGNOJ-UHFFFAOYSA-N
Pubchem ID :57415831

Safety of [ 1138480-98-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 1138480-98-4 ]

* 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 [ 1138480-98-4 ]

[ 1138480-98-4 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 15963-40-3 ]
  • [ 76-02-8 ]
  • [ 1138480-98-4 ]
YieldReaction ConditionsOperation in experiment
61% With copper; zinc; trichlorophosphate; In acetic acid methyl ester; at 0 - 20℃; To a methyl acetate (45 mL) solution of <strong>[15963-40-3]methyl <strong>[15963-40-3]3-methylenecyclobutanecarboxylate</strong></strong> (Intermediate 43A) was added copper powder (2.77 g, 43.6 mmol) and zinc powder (5.70 g, 87 mmol). To this mixture was added a methyl acetate (45 mL) solution of 2,2,2-trichloroacetyl chloride (4.86 mL, 43.6 mmol) and phosphorus oxychloride (0.37 mL, 4.0 mmol) dropwise over 2 h. After 3 h, the reaction was cooled to 0 C, and additional zinc powder (5.70 g, 87 mmol) was added, followed by acetic acid (22.7 mL, 400 mmol) dropwise at a rate keeping the temperature below 7 C. The reaction was allowed to slowly warm to room temperature and after stirring overnight was filtered through Celite, rinsing with EtOAc. The filtrate was carefully washed (warning: gas evolution) with saturated aqueous NaHC03 (2 X 200 mL), and the aqueous layers extracted with 1 :1 EtOAc:Et20 (2 X 100 mL). The combined organic layers were dried over MgS04, filtered and concentrated, and the residue purified on silica gel eluting with a 0%-50% EtOAc-hexanes gradient. The appropriate fractions were combined, evaporated under reduced pressure and placed in vacuo to give the title compound (4.10 g, 61 %) as a yellow oil. 1H NMR (400 MHz, CDCI3) delta 2.38-2.48 (m, 2 H), 2.50-2.61 (m, 2 H), 3.00- 3.09 (m, 2 H), 3.09-3.22 (m, 3 H), 3.68 (s, 3 H).
61% A solution of <strong>[15963-40-3]methyl <strong>[15963-40-3]3-methylenecyclobutanecarboxylate</strong></strong> (5.0 g, 39.6 mmol) was dissolved in dry methyl acetate (45 mL). Copper powder (2.77 g, 43.6 mmol) and zinc powder (5.70 g, 87 mmol) were added to the reaction and the resulting heterogeneous mixture was stirred at room temperature. Next, a solution of 2,2,2-trichloroacetyl chloride (4.86 mL, 43.6 mmol) and phosphorus oxychloride (0.369 mL, 3.96 mmol) in methyl acetate (45 mL) was added dropwise slowly over 2 hours. The reaction mixture was stirred for an additional 3 hours at room temperature. The reaction mixture was then cooled to 0 C and an additional 2.2 equivalents of zinc (5.70 g, 87 mmol) powder was added. Next, a temperature probe was inserted into the reaction and acetic acid (22.69 mL, 396 mmol) was added dropwise keeping the internal temperature of the reaction mixture below 7 C. Total addition time was approximately 15-20 minutes. The reaction was warmed to room temperature and stirred overnight. The reaction mixture was then filtered through a pad of Celite to remove the metals, rinsing with ethyl acetate. The filtrate was diluted with ethyl acetate (100 mL) and stirred vigorously while slowly adding saturated sodium bicarbonate (200 mL). The solution was transferred into a separatory funnel and the layers were separated. The aqueous extracts were then washed with ethyl acetate/diethyl ether (1 :1 , 2 x 100 mL). The organics were combined, dried over magnesium sulfate, filtered, and the solvents removed undervacuum to afford a light brown oil. This material was purified by silica gel chromatography, eluting with 0-50% ethyl acetate in hexanes to afford methyl 6-oxospiro[3.3]heptane-2-carboxylate (4.10 g, 24.38 mmol, 61 % yield) as a clear light yellow oil. 1H NMR (400 MHz, CDCI3) delta 2.43 (m, 2 H), 2.56 (m, 2 H), 3.08 (m, 2 H), 3.13 (m, 3 H), 3.68 (s, 3 H).
 

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