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Chemical Structure| 147959-18-0

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Product Details of [ 147959-18-0 ]

CAS No. :147959-18-0
Formula : C12H23NO4
M.W : 245.32
SMILES Code : O=C(N1C(C)(C)OC[C@@H]1CCO)OC(C)(C)C
MDL No. :MFCD08234429
InChI Key :ZJICPKTZDLBRQH-VIFPVBQESA-N
Pubchem ID :10847957

Safety of [ 147959-18-0 ]

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 [ 147959-18-0 ]

* 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 [ 147959-18-0 ]

[ 147959-18-0 ] Synthesis Path-Downstream   1~7

  • 1
  • [ 77-76-9 ]
  • [ 128427-10-1 ]
  • [ 147959-18-0 ]
YieldReaction ConditionsOperation in experiment
1.96 g With toluene-4-sulfonic acid; In dichloromethane; at 20℃; for 3h; A solution of compound (S)-1 (1.57 g, 11.4 mmol) and triethylamine (1.2 g, 12 mmol) in dry THF was added dropwise to a solution of lithium aluminum hydride (1.74 g, 45.6 mmol) in 20 mL of dry THF at 0 C for 20 min, after which the reaction mixture was refluxed for 4 h. The reaction was quenched with a cold saturated NH4Cl solution (10 mL), after which a 1 M NaOH solution (5 mL) and Boc-anhydride (3.74 g, 17.1 mmol) were added to the reaction mixture and stirred for 30 min. The reaction mixture was filtered and the solvent was evaporated under reduced pressure. The residue was extracted with EtOAc (2 × 20 mL) and dried over anhydrous Na2SO4. After evaporation of the organic extract, the residue was dissolved in dry CH2Cl2 (20 mL). 2,2-Dimethoxypropane (1.38 mL, 11.4 mmol) and cat. PTSA were added and the reaction mixture was stirred at an ambient temperature for 3 h. The organic layer was evaporated under reduced pressure to afford the crude acetonide, which was purified by column chromatography on silica gel (60-120 mesh, EtOAc/hexane, 2:8) to yield 6 (1.96 g, 70%) as a colorless oil (1.96 g, 70%). (c 1, CHCl3). IR (neat): numax 3446, 2931, 2856, 1667, 1451, 1395, 1369, 1253, 1172, 1072, 968, 770 cm-1. 1H NMR (CDCl3, 300 MHz): delta 1.48-1.57 (m, 15H), 1.64-1.85 (m, 2H), 3.44-3.67 (m, 3H), 3.85-3.89 (m, 1H), 3.96-4.01 (m, 1H), 4.16-4.22 (m, 1H). 13C NMR (CDCl3, 75 MHz): delta 24.26, 27.66, 28.24, 37.54, 53.92, 58.59, 68.06, 80.82, 93.52, 153.70. ESIMS: m/z 268.6 [M+Na].+
With toluene-4-sulfonic acid; In dichloromethane; at 18℃; for 2h; Step 1: (S)-tert-butvl 4-(2-hydroxyethyl)-2,2-dimethyloxazolidine-3 -carboxylateTo a solution of (S)-tert-butyl (1 ,4-dihydroxybutan-2-yl)carbamate (3.8 g, 18.51 mmol) in DCM(50 mL) was added 2,2-dimethoxypropane (28.9 g, 278 mmol) and p-toluenesulfonic acidmonohydrate (0.352 g, 1.85 1 mmol) at 18C. The resulting mixture was stirred for 2 hat 18C.TLC (PE/EtOAc=3:1) indicated the reaction was complete. Saturated NaHCO3 (50 mL) was added and the mixture was extracted with DCM (40 mL x 3). The combined organic layers were washed with water (20 mL) and brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified with combi flash (flash column silica-CS (12 g)PE/EtOAc= 100:1 5: 1) to give the title compound.
  • 2
  • [ 147959-18-0 ]
  • [ 147959-19-1 ]
YieldReaction ConditionsOperation in experiment
100% Example 92 (S)-2-[4-(2,3-Dichloro-phenoxy)-2-oxo-2,5-dihydro-pyrrol-1-yl]-N-[1-(2-hydroxy-2-methyl-propyl)-1H-pyrazol-3-yl]-3-(tetrahydro-pyran-2-yl)-propionamide (S)-4-(2-Hydroxy-ethyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester was prepared according to the literature procedure (J. Org. Chem. 2001, 66, 206-215). A solution of dimethylsulfoxide (3.5 mL) in dichloromethane (15 mL) was added dropwise to a cooled solution (-78 C.) of oxalyl chloride (2M in dichloromethane, 13 mL) in dichloromethane (40 mL). The solution was stirred at -60 C. for 15 min before the slow addition of (S)-4-(2-hydroxy-ethyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester (4.5 g, 18.37 mmol) in dichloromethane (20 mL). The mixture was stirred at -60 C. for 30 min and triethylamine (13 mL) was added. After stirring for 30 min, the cooling bath was removed and the mixture was stirred for 1 h at room temperature. The mixture was extracted with dichloromethane and water. The organic layer was dried over sodium sulfate. Solvents were evaporated to give (S)-2,2-dimethyl-4-(2-oxo-ethyl)-oxazolidine-3-carboxylic acid t-butyl ester (4.50 g, 100%) as a colorless oil: 1H NMR (300 MHz, CDCl3) delta ppm 1.42-1.52 (m, 12H), 1.51, 1.63 (2*s, 3H), 2.50-3.16 (m, 2H), 3.73 (d, J=9.1 Hz, 1H), 3.99-4.16 (m, 1H), 4.22-4.44 (m, 1H), 9.79 (s, 1H).
97% A solution of DMSO (5.3 mL, 74.5 mmol) in CH2Cl2 (23 mL) was added dropwise to a cooled solution (-60 C) of oxalyl chloride (3.44 mL, 40.0 mmol) in CH2Cl2 (83 mL). The solution was stirred for 15 min at -60 C, before a solution of alcohol 9 (7.017 g, 28.6 mmol) in CH2Cl2 (36 mL, including rinses) was added slowly. After stirring at -60 0C for 30 min, Et3N (19.9 mL, 142.8 mmol) was added. After 30 min, the cold bath was removed and the reaction was stirred an additional hour at room temperature. The mixture was poured into H2O (360 mL) and extracted with CH2Cl2 (5 x 100 mL). The combined organic layers were washed with H2O (180 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by flash chromatography on silica gel («-hexane/Et2O 1 :1) to afford 6 (6.72O g, 97%) as a colorless solid: mp 34-38 C lit.4 < 40 C; [alpha]22D +35.1 (c l .03, CHCl3) lit.36 [alpha]22D +34.0 (c l.O, CHCl3); 1H NMR (400 MHz, C2D2Cl4, 120 0C): delta 1.47 (s, 9 H), 1.49 (s, 3 H), 1.56 (s, 3 H), 2.63 (dd, J- 7.7, 16.6 Hz, 1 H), 2.88 (dd, J = 4.0, 16.6 Hz, 1 H), 3.70 (bd, J= 9.2 Hz, 1 H), 4.05 (dd, J= 6.0, 9.2 Hz, 1 H), 4.24-4.33 (m, 1 H), 9.77 (bs, 1 H); 13C NMR (100 MHz, C2D2Cl4, 120 0C): delta 24.3 (CH3), 27.1 (CH3), 28.5 (CH3), 48.0 (CH2), 52.8 (CH), 67.8 (CH2), 80.4 (C), 93.9 (C), 151.8 (C), 199.9 (CH).
A solution of DMSO (3.57 mL, 46.2 mmol) in dry dichloromethane (13 mL) was added to a solution of oxalyl chloride (1.83 mL, 20.0 mmol) in dry dichloromethane (50 mL) at -78 C. The reaction mixture was stirred for 15 min at -78 C and a solution of 8 (3.43 g, 14.0 mmol) in dichloromethane (30 mL) was added. The reaction mixture was stirred for another 45 min at -60 C. Next, Et3N (13.3 mL, 95.2 mmol) was then added at -78 C, the cooling bath removed, and the reaction mixture was stirred for 1 h at room temperature. The reaction was quenched by the addition of water and the aqueous phase was extracted with dichloromethane. The combined organic extracts were washed successively with water, aqueous NaHCO3 and brine, dried with Na2SO4, filtered through Celite, and the solvent was removed in vacuo to give the crude aldehyde as a pale yellow oil. This aldehyde was used without any purification for the next step.
At first, DMSO (1.3 mL, 18 mmol) was added to a stirred solution of oxalyl chloride (0.8 mL, 9 mmol), in dry CH2Cl2 (25 mL) at -78 C and stirred at the same temperature for 30 min. A solution of 6 (2.0 g, 8.1 mmol) in dry CH2Cl2 (10 mL) was added at -78 C to the reaction mixture and stirred for 1 h at the same temperature. Next, Et3N (6.8 mL, 49 mmol) was added at -78 C and then stirred for an additional 30 min at rt. The reaction mixture was diluted with water (15 mL) and extracted with dichloromethane (2 × 50 mL). The combined organic layers were washed with brine (50 mL), dried over Na2SO4 and concentrated to obtain the aldehyde as a pale yellow syrup. The aldehyde was used for the next reaction without further purification.
With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; at -78 - 18℃; for 2.1h;Schlenk technique; Step 2: (5)-tert-butyl 2,2-dimethyl-4-(2-oxoethyl)oxazolidine-3 -carboxylateTo a solution of DMSO (1.591 mL, 22.42 mmol) in dry DCM (15 mL) at -78C was added dropwise oxalyl chloride (1.366 g, 10.76 mmol) in a schlenk tube and stirred for 30 mm. A solution of (5)-tert-butyl 4-(2-hydroxyethyl)-2,2-dimethyloxazolidine-3 -carboxylate (2.2 g, 8.97mmol) in 25 mL of DCM was added dropwise. After further stirring at -78C for 30 mi Et3N (7.50 mL, 53.8 mmol) was added dropwise, and then the mixture was warmed to 18C and stirred for 1.6 h. TLC showed the reaction was complete. The mixture was diluted with water (50 mL) and extracted with DCM (60 mL x 3). The combined organic layers were washed with water (50 mL) and brine (40 mL), dried over anhydrous sodium sulfate, filtered and concentratedto give the title compound.
6.06 g With sulfur trioxide pyridine complex; triethylamine; In dimethyl sulfoxide; at 20℃; for 1h; Process obtained in a 3 (S)-tert-butyl 4 - (2-hydroxyethyl) - 2,2-dimethyl-3-carboxylate (5.94g) [...] DMSO (59.4 ml) of triethylamine solution (16.9 ml) and trioxide pyridine complex (12.56g) and added in ambient temperature, copper at a temperature 1 time stirring section. Implanted water sodium bicarbonate saturation reaction mixture, extracted to ethyl acetic acid. Dry magnesium sulfate anhydride organic layer, after filtration, was concentrating. Obtained residue silica gel chromatography (developing solvent: hexane/acetic acid ethyl) for purifying the, title compound 6.06g is obtained.

  • 3
  • [ 77-76-9 ]
  • [ 128427-10-1 ]
  • [ 147959-18-0 ]
  • (S)-N-tert-butoxycarbonyl-2,2-dimethyl-4-hydroxymethyl-1,3-oxazine [ No CAS ]
  • 5
  • [ 128427-10-1 ]
  • [ 147959-18-0 ]
  • 6
  • [ 77-76-9 ]
  • [ 128427-10-1 ]
  • (5S)-2,2-dimethyl-1,3-dioxepane-5-carbaminic acid tert-butyl ester [ No CAS ]
  • [ 850996-87-1 ]
  • [ 147959-18-0 ]
YieldReaction ConditionsOperation in experiment
19%; 16%; 45% toluene-4-sulfonic acid; In dichloromethane; at 20℃; for 36h;Product distribution / selectivity; Dimethoxypropane (1.2 mL, 10 mmol) and /?-toluenesulfonic acid monohydrate (19 mg, 0.1 mmol) were added to a stirred solution of diol 7 (205 mg, 1.0 mmol) in CH2Cl2 (4.5 mL). After stirring for 36 h at room temperature the reaction mixture was poured into saturated aqueous NaHCO3 (5 mL) and extracted with EtOAc (5 x 5 mL). The combined organic layers were dried (MgSO4) and concentrated in vacuo to give a colorless oil. The ratio of 8:9:11 was determined by 1H NMR (500 MHz) to be 30:45:25. The residue was purified by flash chromatography on silica gel («-hexane/EtOAc 80:20 + 0.5% iV-ethyldimethylamine) to afford N,O-acetal 9 (110 mg, 45%) as a colorless solid along with 0,<9-acetal 8 (47 mg, 19%) as a colorless oil and MIP derivative 11 (50 mg, 16%) as a colorless oil, which is prone to hydrolysis.
  • 7
  • [ 79-37-8 ]
  • [ 147959-18-0 ]
  • [ 147959-19-1 ]
YieldReaction ConditionsOperation in experiment
74% With dimethyl sulfoxide; triethylamine; Reference Example 1-56 Synthesis of (2S)-2-amino-5-phenylpentanol (Reference Compound No. 1-56): A methylene chloride solution containing 4.1 ml (46.8 mmol) of oxalyl chloride was cooled to -78C. To this solution, 6.84 ml (97.2 mmol) of dimethyl sulfoxide was added dropwise with stirring. After one hour, a methylene chloride solution containing 9.82 g (40 mmol) of the Reference Compound No. 1-54 synthesised in Reference Example 1-54 was added to the above solution. This reaction solution was further stirred for 3 hours, followed by addition of 27.9 ml (200 mmol) of triethylamine. The reaction mixture was further stirred for 30 minutes. After the temperature of the reaction mixture was raised to room temperature, the reaction mixture was poured into water to separate an organic layer therefrom. The remaining water layer was extracted with methylene chloride, and a mixture of the thus obtained extract layer and the organic layer was washed successively with a 1 N hydrochloric acid solution and a saturated aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure. The residue thus obtained was chromatographed on a silica gel column for purification, whereby 7.15 g of (4S)-2,2-dimethyl-3-(t-butoxycarbonyl)-4-(formylmethyl)-1,3-oxazolidine was obtained in a yield of 74%.
 

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