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Chemical Structure| 929039-94-1 Chemical Structure| 929039-94-1

Structure of 929039-94-1

Chemical Structure| 929039-94-1

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Product Details of [ 929039-94-1 ]

CAS No. :929039-94-1
Formula : C15H12F3NO5S
M.W : 375.32
SMILES Code : O=C(C1=C(O[C@@H](C2=CC=CC=C2C(F)(F)F)C)C=C([N+]([O-])=O)S1)OC
MDL No. :MFCD19443194

Safety of [ 929039-94-1 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P280-P301+P312-P302+P352-P305+P351+P338

Application In Synthesis of [ 929039-94-1 ]

* 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 [ 929039-94-1 ]

[ 929039-94-1 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 79756-81-3 ]
  • [ 89380-77-8 ]
  • [ 929039-94-1 ]
YieldReaction ConditionsOperation in experiment
98% Intermediate Example 1: Methyl 5-amino-3-({(1R)-1-f2-(trifluoromethyl)- phenv?ethylloxy)-2-thiophenecarboxvlate; Step A - Methyl 5-nitro-3-({(1 R)- 1-[2-(trifluoromethyl)phenyl]ethyl}oxy)-2- thiophenecarboxylate; A slurry of polymer-supported triphenylphosphine (62.36 g, 2.21 mmol/g, 137.8 mmol) in DCM (1.0 L) was stirred at room temperature for 10 minutes. The mixture was cooled to 0 0C. Methyl 3-hydroxy-5-nitro-2- thiophenecarboxylate (20.00 g, 98.44 mmol), which may be prepared in a manner analogous to the literature procedure (Barker, J. M.; Huddleston, P. R.; Wood, M. L.; Burkitt, SA Journal of Chemical Research (Miniprint) 200Lambda, 1001-1022) was added, followed by (1 ^-1-[2-(trifluoromethyl)phenyl]ethanol (26.20 g, 137.8 mmol) and di-fe/-butyl azodicarboxylate (31.73 g, 137.8 mmol). The reaction mixture was stirred at room temperature for 21.25 h and then was filtered through a fritted funnel and concentrated. The residue was treated with 4 N HCI in 1 ,4-dioxane (300 ml_) and stirred at room temperature for 3 h. The mixture was then quenched by addition of 3 N sodium hydroxide (300 mL) and saturated aqueous NaHCO3 (200 ml_). The mixture was extracted with DCM (3 x 250 mL). The combined organic fractions were dried over MgSO4, filtered, and concentrated onto silica gel. Purification by column EPO <DP n="41"/>chromatography (0 to 25% EtOAc:hexanes) provided 36.08 g (98%) of the title compound as yellow oil. 1H NMR (300 MHz, CDCI3): delta 7.82 (d, 1H1 J= 7.8 Hz), 7.68 (d, 1 H, J= 7.8 Hz), 7.59 (t, 1H1 J= 7.4 Hz), 7.46 (s, 1 H), 7.42 (t, 1H1 J= 7.6 Hz), 5.77 (q, 1H1 J= 6.1 Hz), 3.94 (s, 3H), 1.74 (d, 3H, J= 6.1 Hz).
98% Step A-Methyl 5-nitro-3-({(1R)-1-[2-(trifluoromethyl)phenyl]ethyl}oxy)-2-thiophenecarboxylate A slurry of polymer-supported triphenylphosphine (62.4 g, 2.21 mmol/g, 138 mmol) in DCM (1.0 L) was stirred at rt for 10 minutes. The mixture was cooled to 0 C. Methyl 3-iiydroxy-5-nitro-2-thiophenecarboxylate (20.0 g, 98.4 mmol), which may be prepared in a manner analogous to the literature procedure (Barker, J. M.; Huddleston, P. R.; Wood, M. L.; Burkiti, S. A. Journal of Chemical Research (Miniprint) 2001, 1001-1022) was added, followed by (1S)-1-[2-(trifluorcmethyl)phenyl]ethanol (26.2 g, 138 mmol) and di-tert-butyl azodicarboxylate (31.7 g, 138 mmol), The reaction mixture was stirred at rt for 21.25 h and then was filtered through a fritted funnel and concentrated. The residue was treated with 4 N HCl in 1,4-dioxane (300 mL) and stirred at rt for 3 h. The mixture was then quenched by addition of 3 N NaOH (300 mL) and saturated aqueous NaHCO3 (200 mL). The mixture was extracted with DCM (3×250 mL). The combined organic fractions were dried over MgSO4, filtered, and concentrated onto silica gel. Purification by column chromatography (0 to 25% EtOAc:hexanes) provided 36.1 g (98%) of the title compound as yellow oil. 1H NMR (300 MHz, CDCl3): delta 7.82 (d, 1H, J=7.8 Hz), 7.68 (d, 1H, J=7.8 Hz), 7.59 (t 1H, J=7.4 Hz), 7.46 (s, 1H), 7.42 (t, 1H, J=7.6 Hz), 5.77 (q, 1H, J=6.1 Hz), 3.94 (s, 3H), 1.74 (d, 3H, J=6.1 Hz).
98% INTERMEDIATE EXAMPLE 1; Methyl 5-amino-3-({(1R)-1-[2-(trifluoromethyl)phenyl]ethyl}oxy)-2-thiophenecarboxylate; Step A-Methyl 5-nitro-3-({(1R)-1-[2-(trifluoromethyl)phenyl]ethyl}oxy)-2-thiophenecarboxylate; A slurry of polymer-supported triphenylphosphine (62.36 g, 2.21 mmol/g, 137.8 mmol) in DCM (1.0 L) was stirred at rt for 10 min. The mixture was cooled to 0 C. Methyl 3-hydroxy-5-nitro-2-thiophenecarboxylate (20.00 g, 98.44 mmol), which may be prepared in a manner analogous to the literature procedure (Barker, J. M.; Huddleston, P. R.; Wood, M. L.; Burkitt, S. A. Journal of Chemical Research (Miniprint) 2001, 1001-1022) was added, followed by (1S)-1-[2-(trifluoromethyl)phenyl]ethanol (26.20 g, 137.8 mmol) and di-tert-butyl azodicarboxylate (31.73 g, 137.8 mmol). The reaction mixture was stirred at rt for 21.25 h and then was filtered through a fritted funnel and concentrated. The residue was treated with 4 N HCl in 1,4-dioxane (300 mL) and stirred at rt for 3 h. The mixture was then quenched by addition of 3 N NaOH (300 mL) and saturated aqueous sodium bicarbonate (200 mL). The mixture was extracted with DCM (3×250 mL). The combined organic fractions were dried over MgSO4, filtered, and concentrated onto silica gel. Purification by column chromatography (0 to 25% EtOAc:hexanes) provided 36.08 g (98%) of the title compound as yellow oil. 1H NMR (300 MHz, CDCl3): delta 7.82 (d, 1H, J=7.8 Hz), 7.68 (d, 1H, J=7.8 Hz), 7.59 (t, 1H, J=7.4 Hz), 7.46 (s, 1H), 7.42 (t, 1H, J=7.6 Hz), 5.77 (q, 1H, J=6.1 Hz), 3.94 (s, 3H), 1.74 (d, 3H, J=6.1 Hz).
98% With di-tert-butyl-diazodicarboxylate; In dichloromethane; at 20℃; for 21.25h; slurry of polymer-supported triphenylphosphine (62.36 g, 2.21 mmol/g, 137.8 mmol) in DCM (1.0 L) was stirred at room temperature for 10 minutes. The mixture was cooled to 0 0C. Methyl 3-hydroxy-5-nitro-2- thiophenecarboxylate (20.00 g, 98.44 mmol), which may be prepared in a manner analogous to the literature procedure (Barker, J. M.; Huddleston, P. R.; Wood, M. L.; Burkitt, S.A. Journal of Chemical Research (Miniprint) 2Q0Lambda , 1001-1022) was added, followed by (1 S)-1-[2-(trifluoromethyl)phenyl]ethanol (26.20 g, 137.8 mmol) and di-t°/T-butyl azodicarboxylate (31.73 g, 137.8 mmol). The reaction mixture was stirred at room temperature for 21.25 h and then was filtered through a fritted funnel and concentrated. The residue was treated with 4 N HCI in 1,4-dioxane (300 mL) and stirred at room temperature for 3 h. The mixture was then quenched by addition of 3 N sodium hydroxide (300 mL) and saturated aqueous NaHCO3 (200 mL). The mixture was extracted with DCM (3 x 250 mL). The combined organic fractions were dried over MgSO4, filtered, and concentrated onto silica gel. Purification by column chromatography (0 to 25% EtOAc:hexanes) provided 36.08 g (98%) of the title compound as yellow oil. 1H NMR (300 MHz, CDCI3): delta 7.82 (d, 1H, J= EPO <DP n="42"/>7.8 Hz), 7.68 (d, 1 H, J= 7.8 Hz), 7.59 (t, 1 H, J= 7.4 Hz), 7.46 (s, 1 H), 7.42 (t, 1 H, J= 7.6 Hz), 5.77 (q, 1 H, J= 6.1 Hz), 3.94 (s, 3H), 1.74 (d, 3H, J= 6.1 Hz).
98% With di-tert-butyl-diazodicarboxylate; In dichloromethane; at 0 - 20℃; for 21.25h; A slurry of polymer-supported triphenylphosphine (62.36 g, 2.21 mmol/g, 137.8 mmol) in dichloromethane (1.0 L) was stirred at room temperature for 10 minutes. The mixture was cooled to 0 C. Methyl 3-hydroxy-5-nitro-2- thiophenecarboxylate (20.00 g, 98.44 mmol), which may be prepared in a manner analogous to the literature procedure (Barker, J. M.; Huddleston, P. R.; Wood, M. L.; Burkitt, S.A. Journal of Chemical Research (Miniprint) 2WLambda , 1001-1022) was added, followed by (1 S)-1-[2-(trifluoromethyl)phenyl]ethanol (26.20 g, 137.8 mmol) and di-terf-butyl azodicarboxylate (31.73 g, 137.8 mmol). The reaction mixture was stirred at room temperature for 21.25 h and then was filtered through a fritted funnel and concentrated. The residue was treated with 4 N HCI in 1 ,4-dioxane (300 ml_) and stirred at room temperature for 3 h. The mixture was then quenched by addition of 3 N sodium hydroxide (300 mL) and saturated aqueous sodium bicarbonate (200 rnL). The mixture was extracted with dichloromethane (3 x 250 mL). The combined organic fractions were dried over magnesium sulfate, filtered, and concentrated onto silica gel. Purification by column chromatography (0 to 25% ethyl acetate:hexanes) provided 36.08 g (98%) of the title compound as yellow oil. 1H NMR (300 MHz, CDCI3): 57.82 (d, 1H, J= 7.8 Hz)1 7.68 (d, 1H, J= 7.8 Hz), 7.59 (t, 1 H, J= 7.4 Hz), 7.46 (s, 1 H), 7.42 (t, 1H, J= 7.6 Hz), 5.77 (q, 1 H, J= 6.1 Hz)1 3.94 (S1 3H)1 1.74 (d, 3H, J= 6.1 Hz).
98% With triphenylphosphine on polystyrene; di-tert-butyl-diazodicarboxylate; In dichloromethane; at 0 - 20℃; for 21.25h; Intermediate 29: Methyl delta-ami?o-3-{{{1 ff)-1-|[2- (trifluoromethyi)phe?yi|ethyi}oxy)-2-thiophenec3rboxyiateStep A - Methyl 5-nitro-3-({(1/t)-1-(2-(trifluoiOmethyl)phenyl]ethyl}o>cy)-2- thiophenecarboxyiateA slurry of polymer-supported triphenySphosphi?e (82.4 g, 2.21 r?mol/g, 138 r?mol) in DCM (1.0 L) was stirred at for 10 minutes. The mixture was cooled to 0 0G. Methyl 3-hydroxy-5-nitra-2-thiophenecartoxy.ate (20.0 g, 98.4 mmol), which may be prepared in 8 manner analogous to the literature procedure{Barker, J. M.; Huddleston, P. R.; Wood, M.L.; Burkitt, S.A. Journal of Chemical Research (M/nphirintJIQQt, 1001-1022) was added, followed by {1 S)-I-[Z- {trifliioromethyi)phenyl]ethano. (28.2 g, 138 mmol) and di-t°/f butyl azodicarboxylate (31.7 Q3 138 mmoi). The reaction mixture was stirred at it for 21.25 h and then was filtered through a fritted funnel and concentrated. The <n="124"/>residue was treated with 4 N HC. in 1 ,4-dioxa?e (300 ml) and stirred at rt for 3 h, The mixture was then quenched by addition of 3 N NaOH (300 ml_) and saturated aqueous NaHCO3 (200 ml). The mixture was extracted with DCM (3 x 250 rnL). The combined organic fractions were dried over IVIgSO4, filtered, and concentrated onto silica gel Purification by column chromatography (0 to 25% EtOAc:hexanes) provided 36.1 g (98%) of the title compound as yellow oil. 1H NlVIR (300 MHz1 CDCb): 6 7.82 (d, 1H, J= 7.8 Hz), 7.68 (d, I H1 J= 7,8 Hz), 7,59 (t, 1 H1 J^ 7.4 Hz), 7.46 (s, I H), 7.42

  • 2
  • [ 79756-81-3 ]
  • [ 89380-77-8 ]
  • [ 929039-94-1 ]
 

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