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Chemical Structure| 393536-19-1 Chemical Structure| 393536-19-1

Structure of 393536-19-1

Chemical Structure| 393536-19-1

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Product Details of [ 393536-19-1 ]

CAS No. :393536-19-1
Formula : C12H27NO2SSi
M.W : 277.50
SMILES Code : CC([S@](/N=C/CO[Si](C)(C(C)(C)C)C)=O)(C)C
MDL No. :N/A

Safety of [ 393536-19-1 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319
Precautionary Statements:P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330

Application In Synthesis of [ 393536-19-1 ]

* 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 [ 393536-19-1 ]

[ 393536-19-1 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 30506-30-0 ]
  • [ 393536-19-1 ]
  • (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]
  • (R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (1.88 g, 8.65 mmol) in anhydrous THF (15 mL) was added n-BuLi (14.4 mL, 36.0 mmol, 2.5 M in THF) at -78 C. under N2. The reaction mixture was stirred at -78 C. for 0.5 h, then a solution of (R,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (2.0 g, 7.2 mmol) in THF (1 mL) was added dropwise to the mixture at -78 C. The reaction mixture was stirred at -78 C. for 0.5 h and was allowed to warm to rt. After 0.5 h at rt, the reaction mixture was quenched with water (10 mL) and extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with H2O (10 mL) then brine (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by column chromatography on silica gel (eluting with a gradient of 5% to 10% ethyl acetate in petroleum ether) to afford a 3:2 mixture of (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (2.86 g, 47.9%) as a yellow oil. This 3:2 mixture of diastereomers was used for the subsequent reactions. 1H NMR (CDCl3 400 MHz): δ 7.24-7.16 (m, 4H), 4.47-4.40 (m, 1H), 4.21 (s, 1H), 3.75-3.67 (m, 1H), 3.60-3.47 (m, 1H), 2.90 (q, J=7.2 Hz, 2H), 1.27 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.85 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).
To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (1.88 g, 8.65 mmol) in anhydrous THF (15 mL) was added n-BuLi (14.4 mL, 36.0 mmol, 2.5 M in THF) at -78 C under N2. The reaction mixture was stirred at -78 C for 0.5 h, then a solution of (R,E)-N-(2-((tert- butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (2.0 g, 7.2 mmol) in THF (1 mL) was added dropwise to the mixture at -78 C. The reaction mixture was stirred at -78 C for 0.5 h and was allowed to warm to rt. After 0.5 h at rt, the reaction mixture was quenched with water (10 mL) and extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with H2O (10 mL) then brine (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by column chromatography on silica gel (eluting with a gradient of 5% to 10% ethyl acetate in petroleum ether) to afford a 3:2 mixture of (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide and (R)-N-((S)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (2.86 g, 47.9 %) as a yellow oil. This 3:2 mixture of diastereomers was used for the subsequent reactions. 1H NMR (CDCl3 400 MHz): δ 7.24-7.16 (m, 4H), 4.47-4.40 (m, 1H), 4.21 (s, 1H), 3.75-3.67 (m, 1H), 3.60-3.47 (m, 1H), 2.90 (q, J = 7.2 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H), 1.18 (s, 9H), 0.85 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).
  • 2
  • [ 30506-30-0 ]
  • [ 393536-19-1 ]
  • (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% [00148] To a solution of (4-bromophenyl) (ethyl) sulfane (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise w-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at -78 C. The mixture was stirred at -78 C for 30 min. A solution of (R,E)-N-(2- ((ieri-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at - 78 C for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with saturated aqueous NH4CI solution (200 mL) and extracted with ethyl acetate (3 x 300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether: ethyl acetate = 15: 1) three times to afford (R)-N-((R)-2-((ieri-butyldimethylsilyl)oxy)- 1- (4-(ethylthio)phenyl)ethyl)-2- methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDC13, 400 MHz): δ 7.21-7.24 (d, J = 7.2 Hz, 2H), 7.18-7.21 (d, J = 8.4 Hz, 2H), 4.42-4.45 (dd, J = 8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J = 10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J = 9.6 Hz, 1H), 2.87- 2.92 (q, J = 1.6 Hz, 2H), 1.25- 1.29 (t, J = 1.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LCMS tR = 1.010 min in 5-95AB_1.5 min chromatography (MK RP18e 25-2mm), MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR = 3.607 and 4.014 min in 12 min chromatography (AD- H_5_5_40_2.3 5 ML), ee = 90.85%.
44% To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise n-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at -78 C. The mixture was stirred at -78 C. for 30 min. A solution of (R,E)-N-(2-((tert-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at -78 C. for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with saturated aqueous NH4Cl solution (200 mL) and extracted with ethyl acetate (3×300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether:ethyl acetate=15:1) three times to afford (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDCl3, 400 MHz): δ 7.21-7.24 (d, J=7.2 Hz, 2H), 7.18-7.21 (d, J=8.4 Hz, 2H), 4.42-4.45 (dd, J=8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J=10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J=9.6 Hz, 1H), 2.87-2.92 (q, J=7.6 Hz, 2H), 1.25-1.29 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LCMS tR=1.010 min in 5-95AB_1.5 min chromatography (MK RP18e 25-2 mm), MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR=3.607 and 4.014 min in 12 min chromatography (AD-H_5_5_40_2.3 5 ML), ee=90.85%.
44% To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g,133.1 mmol) in anhydrous THF (500 mE) was addeddropwise n-butyllithium (73 mE, 181.5 mmol, 2.5 M inhexanes) at -78 C. The mixture was stirred at -78 C. for30 mm. A solution of (R,E)-N-(2-((teit-butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g,121 mmol) in anhydrous THF (100 mE) was added to themixture at -78 C. The mixture was stirred at -78 C. for 2h, then allowed to warm to it and stirred for 2 h. The mixturewas quenched with saturated aqueous NH4C1 solution (200mE) and extracted with ethyl acetate (3x300 mE). Thecombined organic layer was washed with water (200 mE)and brine (200 mE), dried over anhydrous Na2SO4, filteredand concentrated under vacuum. The residue was purified bysilica gel chromatography (eluting with petroleum ether:ethyl acetate=1 5:1) three times to afford (R)-N-((R)-2-((teit-butyldimethylsilyl)oxy)-1 -(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as ayellow oil. ‘H NMR (CDC13, 400 MHz): ö 7.21-7.24 (d,J=7.2 Hz, 2H), 7.18-7.21 (d, J=8.4 Hz, 2H), 4.42-4.45 (dd,J=8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J=10.4, 4.4Hz, 1H), 3.51-3.56 (t, J=9.6 Hz, 1H), 2.87-2.92 (q, J=7.6 Hz,2H), 1.25-1.29 (t, J=7.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H),0.02 (s, 6H). ECMS tR=1.010 mm in 5-95A13_1.5 mm chromatography (MK RP1 8e 25-2 mm), MS (ESI) mlz 437.9 [M+Na]t Isomer SFC tR=3.607 and 4.014 mm in 12mm chromatography (AD-H_5_5_40_2.3 5 ME), ee=90.85%.
44% [00208] To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise n-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at - 78 C. The mixture was stirred at -78 C for 30 min. A solution of (R,E)-N-(2-((tert- butyldimethylsilyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at -78 C for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with satd aq NH4C1 solution (200 mL) and extracted with EtOAc (3 x 300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether: EtOAc = 15: 1) three times to afford (R)-N-((R)-2-((tert- butyldimethylsilyl)oxy)- l- (4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDCI3, 400 MHz): δ 7.21-7.24 (d, J = 1.2 Hz, 2H), 7.18-7.21 (d, J = 8.4 Hz, 2H), 4.42-4.45 (dd, J = 8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J = 10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J = 9.6 Hz, 1H), 2.87-2.92 (q, J = 7.6 Hz, 2H), 1.25-1.29 (t, J = 1.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LC-MS Method 3 tR = 1.010 min MS (ESI) m/z 437.9 [M+Na]+. Isomer SFC tR = 3.607 and 4.014 min in 12 min chromatography (AD- H55402.3 5 ML), ee = 90.85%.

  • 3
  • [ 30506-30-0 ]
  • [ 393536-19-1 ]
  • (R)-N-((R)-2-((tert-butyldimethylsilyl)oxy)-1-(4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% To a solution of <strong>[30506-30-0](4-bromophenyl)(ethyl)sulfane</strong> (28.9 g, 133.1 mmol) in anhydrous THF (500 mL) was added dropwise n-butyllithium (73 mL, 181.5 mmol, 2.5 M in hexanes) at - 78 C. The mixture was stirred at -78 C for 30 mm. A solution of (R,E)-N-(2-((tert- butyldimethyl silyl)oxy)ethylidene)-2-methylpropane-2-sulfinamide (33.5 g, 121 mmol) in anhydrous THF (100 mL) was added to the mixture at -78 C. The mixture was stirred at -78 C for 2 h, then allowed to warm to rt and stirred for 2 h. The mixture was quenched with saturated aqueous NH4C1 solution (200 mL) and extracted with ethyl acetate (3 x 300 mL). The combined organic layer was washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2504, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography (eluting with petroleum ether: ethyl acetate = 15:1) three times to afford (R)-N59 ((R)-2-(Qert-butyldimethyl silyl)oxy)- 1- (4-(ethylthio)phenyl)ethyl)-2-methylpropane-2-sulfinamide (22 g, 44%) as a yellow oil. 1H NMR (CDC13, 400 IVIHz): (57.21-7.24 (d, J= 7.2Hz, 2H), 7.18-7.21 (d, J= 8.4 Hz, 2H), 4.42-4.45 (dd, J= 8.8, 2.4 Hz, 1H), 4.21 (brs, 1H), 3.69-3.73 (dd, J 10.4, 4.4 Hz, 1H), 3.51-3.56 (t, J 9.6 Hz, 1H), 2.87-2.92 (q, J= 7.6 Hz, 2H), 1.25-1.29 (t, J= 7.2 Hz, 3H), 1.18 (s, 9H), 0.88 (s, 9H), 0.02 (s, 6H). LCMS tR = 1.0010 mm in 5-95AB1.5 mm chromatography (IVIK RP18e 25-2mm), MS (ESI) m/z 437.9 [M+Na]. IsomerSFC tR= 3.607 and 4.0014 mm in 12 mm chromatography (AD-H 5 540 2.3 5 ML), ee =90.85%.
 

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