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Chemical Structure| 853269-57-5 Chemical Structure| 853269-57-5

Structure of 853269-57-5

Chemical Structure| 853269-57-5

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Product Details of [ 853269-57-5 ]

CAS No. :853269-57-5
Formula : C15H24N2O5S
M.W : 344.43
SMILES Code : O=C(OC(C)(C)C)N[C@@]1(C(NS(=O)(C2(C)CC2)=O)=O)[C@H](C=C)C1
MDL No. :MFCD21496656
Boiling Point : No data available

Safety of [ 853269-57-5 ]

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 [ 853269-57-5 ]

* 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 [ 853269-57-5 ]

[ 853269-57-5 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 159622-10-3 ]
  • [ 853269-57-5 ]
YieldReaction ConditionsOperation in experiment
77% With CDI; 1,8-diazabicyclo[5.4.0]undec-7-ene; In tetrahydrofuran; Step B: Synthesis of tert-butyl (1R,2S)-1-(1-methylcyclopropylsulfonyl-carbamoyl)-2-vinylcyclopropylcarbamate 122. Compound 121 (104.6 g) was dissolved in THF (1.0 L) at room temperature under argon. CDI (1.5 eq.) was added and the reaction mixture was refluxed for 20 min. After the reaction mixture was cooled to 4-6° C., sulfonamide (1.5 eq.) was added, followed by the addition of DBU (2 eq.). After stirring at room temperature for 64 hrs, the reaction mixture was diluted with DCM, neutralized with 1M HCl, and washed with saturated brine to pH 7. The organics were dried over sodium sulfate and concentrated to give an off-white solid in 106.4 g. Crystallization from methanol/water gave compound 122 (91 g) as a white solid in 77percent yield.
  • 2
  • [ 669008-26-8 ]
  • [ 159622-10-3 ]
  • [ 853269-57-5 ]
YieldReaction ConditionsOperation in experiment
79% To a solution of lR-tert-butoxycarbonylamino-2S-vinyl-cyclopropanecarboxylic acid (2.3 g, 10.1 mmol) in THF (40 mL) was added CDI (1.80 g, 11.6 mmol) and was heated to 85 °C for 30 min. After let cool to rt, the reaction mixture was treated with 1-methyl-cyclopropanesulfonam (1.64 g, 12.1 mmol) and DBU (3.08 g, 20.2 mmol). After stirring at rt for 16 h, the reaction was diluted with EtOAc (160 mL) and washed with 2x25 mL IN HC1. The combined aqueous layer was extracted with 1x50 mL EtOAc. The combined organic layer was washed with H20 (50 mL), brine, dried over MgS04 and concentrated to a light yellow solid product (2.75 g, 79percent). The product was used as crude. MS m/z 367 (M+Na).
74.2% General procedure: Step 2: tert-butyl ((lR,2S)-l-(((l-methylcyclopropyl)sulfonyl)carbamoyl)-2- vinylcyclopropyl)carbamate A round-bottom flask was charged with the carboxylic acid product of step 1 (2 g, 8.80 mmol) and Iota,Gamma-carbonyldiimidazole (2.141 g, 13.20 mmol). Dry THF (44.0 ml) was added under anhydrous conditions and the mixture was heated (oil bath at 85°C) for 2 hours with exclusion of moisture. The mixture was cooled to room temp and a solution of 1- methylcyclopropane-1 -sulfonamide (2.379 g, 17.60 mmol) in dry THF (10 mL) was added followed by l,8-diazabicyclo[5.4.0]undec-7-ene (2.63 ml, 17.60 mmol). The mixture was heated (oil bath at 75°C) overnight. The reaction mixture was treated with aq 1M HC1 (20 mL) and water (50 mL). The product was extracted into ethyl acetate (400 mL). Upon separation, the organic layer was washed with aq 1M HCl/water (1 :2, 80 mL), and brine (80 mL), dried over magnesium sulfate, filtered and concentrated in rotavap. The residue was purified on a gold cap RediSep® (120 g) silica gel column (gradient: 0 to 25percent ethyl acetate in dichloromethane) to give the the title compound (2.25 g, 6.53 mmol, 74.2 percent yield) as a white powder.
74.2% A round-bottom flask was charged with the carboxylic acid product of step 1 (2 g, 8.80 mmol) and 1,1?-carbonyldiimidazole (2.141 g, 13.20 mmol). Dry THF (44.0 ml) was added under anhydrous conditions and the mixture was heated (oil bath at 85° C.) for 2 hours with exclusion of moisture. The mixture was cooled to room temp and a solution of 1-methylcyclopropane-1-sulfonamide (2.379 g, 17.60 mmol) in dry THF (10 mL) was added followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (2.63 ml, 17.60 mmol). The mixture was heated (oil bath at 75° C.) overnight. The reaction mixture was treated with aq 1M HCl (20 mL) and water (50 mL). The product was extracted into ethyl acetate (400 mL) Upon separation, the organic layer was washed with aq 1M HCl/water (1:2, 80 mL), and brine (80 mL), dried over magnesium sulfate, filtered and concentrated in rotavap. The residue was purified on a gold cap RediSep® (120 g) silica gel column (gradient: 0 to 25percent ethyl acetate in dichloromethane) to give the title compound (2.25 g, 6.53 mmol, 74.2percent yield) as a white powder.
65% Carbonyldiimidazole (1.75 g, 1.3 eq.) was added to a solution of compound 32B (1.89 g, 1 eq.) in anhydrous THF (20 mL) at room temperature. The reaction mixture was refluxed for 2 hrs and allowed to cooled down to room temperature. Methyl cyclopropyl sulfonamide (1.68 g, 1.5 eq.) and DBU (1.68 g, 1.5 eq.) were then added at 0 0C and the mixture was stirred at room temperature for 16 hrs.Solvent was removed in vacuo and the residue was dissolved in EtOAc, washed sequentially with IN HCl and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure to yield compound 32Ca as a white powder in 65percent yield. 1H NMR (CDCl3, 400 MHz) delta (ppm) 1.01-1.05 (m, 2H), 1.25-1.28 (m, 2H), 1.35-1.40 (m, 2H), 1.45 (s, 9H), 1.50 (s, 3H), 1.77-1.80 (m, IH), 4.90(d, J= 10.60 Hz, IH), 5.04 (d, J= 17.32 Hz, IH), 5.42 (m, IH).
58% To a solution of <strong>[159622-10-3](1R,2S)-1-(tert-butoxycarbonylamino)-2-vinylcyclopropanecarboxylic acid</strong> (25 g, 110 mmol) in THF (300 mL) was added CDI (205 g, 127 mmol) and the reaction mass was heated at 85° C. for 1 h. The reaction mass was cooled to rt and to this reaction mass was added 1-methylcyclopropane-1-sulfonamide (17.7 g, 131 mmol) followed by DBU (33.2 mL, 33.5 mmol). The reaction mixture was stirred at rt for 18 h. The solvent was evaporated under reduced pressure and the residue was diluted with water and acidified to pH ?2 by using aq. 1.5 N HCl solution. The precipitated solid was isolated via filtration and washed with water to get desired compound (22 g, 58percent) as off-white solid. 1H NMR (400 MHz, DMSO-d6) delta ppm 11.01-11.17 (m, 1H), 7.17-7.33 (m, 1H), 5.35-5.51 (m, 1H), 5.18-5.29 (m, 1H), 4.99-5.09 (m, 1H), 2.21 (s, 1H), 1.69 (dd, J=7.78, 5.27 Hz, 1H), 1.40 (d, J=3.01 Hz, 14H), 1.20 (dd, J=9.29, 5.27 Hz, 1H), 0.82-0.96 (m, 2H). MS: MS m/z 343 (M++1).
Step 4: tert-butyl [(lR,2S)-2-ethenyl-l~[(l-methylcyclopropyl)sulfonyl]carbamoyl}cyclopropyl] carbamate; To a solution of (li?,2<S)-l-[(ter/-butoxycarbonyl)amino)-2- ethenylcyclopropanecarboxylic acid (4.35 g, 19.1 mmol) in THF (75 mL), carbonyldiimidazole (4.0 g, 24.88 mmol) was added, and the solution was then heated to reflux for 1 hour. The mixture was then cooled to T, and the product from step 3 (4.35 g, 19.14 mmol) was then added followed by DBU (4.0 mL, 26.8 mmol). After stirring for 20 hours, 1 N HC1 was added until acidic, and the mixture was extracted with EtO Ac 2x. The combined organic layers were dried over Na2S04, and the solvent was removed in vacuo. 1 : 1 EtOAc/hexanes (100 mL) was then added, and the resulting solid was filtered. The filtrate was concentrated and the 1 : 1 EtOAc hexanes was added again to produce more solid. The combined solids were dried to yield the title compound as a solid (5 g). LCMS (ES+) m/z 289.3 ((M-/-Bu) +H)+.
With hydrogenchloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,1'-carbonyldiimidazole; In tetrahydrofuran; Preparation of tert-butyl ((1R,2S)-1-(((1-methylcyclopropyl)sulfonyl)carbamoyl)-2-vinylcyclopropyl)carbamate To a solution of <strong>[159622-10-3](1R,2S)-1-(tert-butoxycarbonylamino)-2-vinylcyclopropanecarboxylic acid</strong> (25 g, 110 mmol) in THF (300 mL) was added CDI (205 g, 127 mmol) and the reaction mass was heated at 85° C. for 1 h. The reaction mass was cooled to rt and to this reaction mass was added 1-methylcyclopropane-1-sulfonamide (17.7 g, 131 mmol) followed by DBU (33.2 mL, 33.5 mmol). The reaction mixture was stirred at rt for 18 h. The solvent was evaporated under reduced pressure and the residue was diluted with water and acidified to pH ?2 by using aq. 1.5 N HCl solutions. The precipitated solid was isolated via filtration and washed with water to get desired compound (22 g, 58percent) as off-white solid. 1H NMR (400 MHz, DMSO-d6) delta ppm 11.01-11.17 (m, 1H), 7.17-7.33 (m, 1H), 5.35-5.51 (m, 1H), 5.18-5.29 (m, 1H), 4.99-5.09 (m, 1H), 2.21 (s, 1H), 1.69 (dd, J=7.78, 5.27 Hz, 1H), 1.40 (d, J=3.01 Hz, 14H), 1.20 (dd, J=9.29, 5.27 Hz, 1H), 0.82-0.96 (m, 2H). MS:MS m/z 343 (M++1).

 

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