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Chemical Structure| 31469-29-1 Chemical Structure| 31469-29-1

Structure of 31469-29-1

Chemical Structure| 31469-29-1

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Product Details of [ 31469-29-1 ]

CAS No. :31469-29-1
Formula : C7H14O2Si
M.W : 158.27
SMILES Code : O=C(C1([Si](C)(C)C)CC1)O
MDL No. :MFCD09868747

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Application In Synthesis of [ 31469-29-1 ]

* 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 [ 31469-29-1 ]

[ 31469-29-1 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 718632-46-3 ]
  • [ 31469-29-1 ]
  • ethyl 6,6-dimethyl-3-[1-(trimethylsilyl)cyclopropanecarboxamido]-5,6-dihydropyrrolo[3,4-c]pyrazole-2(4H)-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% To a solution of 9.70 g (61.3 mmol) of 1-(trimethylsilyl)cyclopropanecarboxylic acid [synthesized according to the method described in J. Org. Chem., 1982 (47) 5, 893-895] in 120 ml of dehydrated dichloromethane, 6.60 ml (76.9 mmol) of oxalyl chloride and 0.25 ml (3.2 mmol) of dehydrated DMF were added in this order at 0C in a nitrogen atmosphere and then stirred for 2.5 hours with the temperature unchanged. After the completion of the reaction, the reaction solution was concentrated under reduced pressure and dried under reduced pressure to obtain a concentration residue. To a solution of 19.0 ml (109 mmol) of DIPEA and 9.94 g (30.6 mmol) of <strong>[718632-46-3]5-tert-butyl 2-ethyl 3-amino-6,6-dimethylpyrrolo[3,4-c]pyrazole-2,5(4H,6H)-dicarboxylate</strong> [synthesized according to the method described in Journal of Medicinal Chemistry 2012, 55 (10), 4728-4739] in 170 ml of dehydrated dichloromethane, a solution of the obtained concentration residue in 30 ml of dehydrated dichloromethane was added at 0C in a nitrogen atmosphere and then stirred for 24 hours with the temperature unchanged. After the completion of the reaction, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution and stirred, followed by extraction with dichloromethane once and ethyl acetate twice. All of the obtained organic layers were dried over anhydrous magnesium sulfate, then filtered, and concentrated under reduced pressure. The obtained concentration residue was subjected to silica gel column chromatography (elution solvent: n-hexane:ethyl acetate = 90:10 to 70:30 (V/V)), and a fraction containing the compound of interest was concentrated under reduced pressure. A concentration residue of a fraction containing impurities was subjected again to silica gel column chromatography (elution solvent: n-hexane:ethyl acetate = 90:10 to 75:25 (V/V)), combined with the purified form obtained above, concentrated under reduced pressure, and dried under reduced pressure to obtain 10.63 g of a concentration residue. To a solution of the obtained concentration residue in 100 ml of ethyl acetate, 60.0 ml (240 mmol) of 4 N hydrogen chloride/ethyl acetate was added at room temperature in a nitrogen atmosphere and then stirred for 5 hours with the temperature unchanged. After the completion of the reaction, the reaction solution was concentrated under reduced pressure. The obtained concentration residue was suspended in diisopropyl ether, and the suspension was stirred at room temperature. Insoluble matter was collected by filtration, and the obtained solid was washed with diisopropyl ether. The obtained solid was dissolved in water, and then, a saturated aqueous solution of sodium bicarbonate and dichloromethane were added and stirred at room temperature for 5 minutes. After separation into an aqueous layer and an organic layer, the aqueous layer was subjected to extraction with dichloromethane twice. All of the organic layers were washed with a saturated aqueous solution of sodium chloride, then dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and dried under reduced pressure to obtain 8.27 g of the title compound (yield: 73% [2 steps]) as a light orange solid. Mass spectrum (DUIS, m/z): 365 [M+1]+. 1H-NMR spectrum (400 MHz, CDCl3) delta: 10.02 (s, 1H), 4.53 (q, J = 7.2 Hz, 2H), 4.16 (s, 2H), 1.50 - 1.43 (m, 9H), 1.14 - 1.08 (m, 2H), 0.84 - 0.77 (m, 2H), 0.12 (s, 9H).
  • 2
  • [ 718632-46-3 ]
  • [ 31469-29-1 ]
  • 5-tert-butyl 2-ethyl 6,6-dimethyl-3-[1-(trimethylsilyl)cyclopropanecarboxamido]pyrrolo[3,4-c]pyrazole-2,5(4H,6H)-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1.19 g To a solution of 1.05 g (6.63 mmol) of 1-(trimethylsilyl)cyclopropanecarboxylic acid [synthesized according to the method described in ] in 20 ml of dehydrated dichloromethane, 0.70 ml (8.2 mmol) of oxalyl chloride and 0.020 ml (0.26 mmol) of DMF were added at 0C in a nitrogen atmosphere and stirred at the same temperature as above for 3 hours. After the completion of the reaction, the reaction solution was concentrated under reduced pressure (hot water bath temperature: 25C) to obtain a concentration residue. To a solution of the obtained concentration residue in 15 ml of dehydrated dichloromethane, 1.80 ml (10.3 mmol) of DIPEA and 839 mg (2.59 mmol) of <strong>[718632-46-3]5-tert-butyl 2-ethyl 3-amino-6,6-dimethylpyrrolo[3,4-c]pyrazole-2,5(4H,6H)-dicarboxylate</strong> [synthesized according to the method described in ] were added at 0C in a nitrogen atmosphere and stirred at the same temperature as above for 20.5 hours. After the completion of the reaction, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution, followed by extraction with dichloromethane twice. All of the obtained organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentration residue was subjected to silica gel column chromatography (elution solvent: n-hexane:ethyl acetate = 90:10 to 75:25 (V/V)), and a fraction containing the compound of interest was concentrated under reduced pressure and dried under reduced pressure to obtain 1.19 g of the title compound (containing impurities) as a pale yellow foam. Mass spectrum (CI, m/z): 465 [M+1]+. 1H-NMR spectrum (400 MHz, CDCl3) delta: 10.09 & 9.92 (s, total 1H), 4.70 - 4.46 (m, 4H), 1.72 (s, 3H), 1.65 (s, 3H), 1.54 - 1.44 (m, 12H), 1.15 - 1.07 (m, 2H), 0.84 - 0.78 (m, 2H), 0.17 - 0.07 (m, 9H).
To a solution of 9.70 g (61.3 mmol) of 1-(trimeth- ylsilyl)cyclopropanecarboxylic acid [synthesized according to the method described in J. Org. Chem., 1982(47) 5, 893-895] in 120 ml of dehydrated dichloromethane, 6.60 ml (76.9 mmol) of oxalyl chloride and 0.25 ml (3.2 mmol) of dehydrated DMF were added in this order at 00 C. in a nitrogen atmosphere and reacted at 00 C. for 2.5 hours with stirring. After completion of the reaction, the reaction solution was concentrated under reduced pressure and dried under reduced pressure. A solution of the obtained concentration residue in 30 ml of dehydrated dichloromethane was added to a solution of 19.0 ml (109 mmol) of DIPEA and 9.94 g (30.6 mmol) of 5-tert-butyl 2-ethyl 3-amino-6,6- dimethylpyrrolo[3,4-c]pyrazole-2,5(4H,6H)-dicarboxylate[synthesized according to the method described in Journal of Medicinal Chemistry 2012, 55 (10), 4728-4739] in 170 ml of dehydrated dichioromethane at 00 C. in a nitrogen atmosphere and reacted at 00 C. for 24 hours with stirring. After completion of the reaction, a saturated aqueous solution of sodium bicarbonate was added to the reaction solution and stirred, followed by extraction once with dichloromethane and twice with ethyl acetate. The whole organic layer thus obtained was dried over anhydrous magnesium sulfate, then filtered, and concentrated under reduced pressure. The obtained concentration residue was subjected to preparative column chromatography (apparatus 2, silica gel, elution solvent: n-hexane:ethyl acetate=90: 10-70:30 (V/V)), and a fraction containing 5-tert-butyl 2-ethyl 6,6- dimethyl-3-[1 -(trimethylsilyl)cyclopropanecarboxamido]pyrrolo[3,4-c]pyrazole-2,5(4H,6H)-dicarboxylate was concentrated under reduced pressure. The concentration residue of the fraction containing impurities was subjected again to preparative column chromatography (apparatus 2, silica gel, elution solvent: n-hexane: ethyl acetate=90: 1 0-75 :25 (V/V)), combined with the preliminarily obtained fraction, concentrated under reduced pressure, and dried under reduced pressure.
 

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