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Structure of 141699-66-3

Chemical Structure| 141699-66-3

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Product Details of [ 141699-66-3 ]

CAS No. :141699-66-3
Formula : C12H21NO3S
M.W : 259.37
SMILES Code : O=C(N1CCC(SC(C)=O)CC1)OC(C)(C)C
MDL No. :MFCD13183580

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Application In Synthesis of [ 141699-66-3 ]

* 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 [ 141699-66-3 ]

[ 141699-66-3 ] Synthesis Path-Downstream   1~3

  • 1
  • sodium methoxide-methanol [ No CAS ]
  • [ 141699-66-3 ]
  • [ 134464-79-2 ]
YieldReaction ConditionsOperation in experiment
With acetic acid; In methanol; Reference Example 12 1-(tert-Butoxycarbonyl)-4-mercaptopiperidine STR254 In dry methanol were dissolved 520 mg (2 mmol) of 4-(acetylthio)-1-(tert-butoxycarbonyl)piperidine, and 420 μl (2 mmol) of a 28% sodium methoxide-methanol solution were added to the mixture under ice-cooling and under a nitrogen atmosphere, followed by stirring of the resulting mixture for 40 minutes. Then, 173 μl of acetic acid were added to the mixture and the solvent was distilled off at room temperature, followed by diluting of the residue with ethyl acetate. The mixture was washed successively with an aqueous sodium hydrogencarbonate solution and an aqueous NaCl solution in the order and the solvent was distilled off to obtain 430 mg of reddish orange oil. This product was used for a subsequent reaction without purification. NMR spectrum (270 MHz, CDCl3) δ ppm: 1.46 (9H, s), 1.5-1.6 (2H, m), 1.9-2.0 (2H, m), 2.8-3.0 (3H, m), 3.9-4.1 (2H, m). Mass spectrum m/e: 217, 202, 184, 161, 144, 127, 117, 84, 82.
  • 2
  • [ 141699-66-3 ]
  • [ 134464-79-2 ]
YieldReaction ConditionsOperation in experiment
89% With sodium tetrahydridoborate; In methanol; at 0 - 20℃; for 16h; To a stirred solution of tert-butyl 4-(acetylthio)piperidine-1-carboxylate (8 g, 30.88 mmol, 1eq.) in methanol (80 mL) was added sodium borohydride (8.17 g, 21.62 mmol, 7 eq.) portion wise at 0 C. Reaction mixture was allowed to room temperature and stirred for 16 h. After complete conversion by TLC, reaction mixture was concentrated under reduced pressure. The residue was carefully dissolved in water and acidified with citric acid (pH = 6). The product was extracted with dichloromethane (2 X 100 mL), the extracts combined, dried over sodium sulfate, filtered and the filtrate evaporated in vacuum obtained the tert-butyl 4-mercaptopiperidine-1-carboxylate as a brown oil (6 g, 89%). TLC system: EtOAc/hexane (1:4), Rf value: ~ 0.4, KMnO4 stain+ve.1HNMR (400 MHz, DMSO-d6) δ 3.81-3.77 (m, 2H), 2.93-2.83 (m, 3H), 2.65 (d, J = 7.2 Hz, 1 H) 1.88-1.85 (m, 2H), 1.30-1.32 (m, 2H), 1.38 (s, 9H).
89% With sodium tetrahydridoborate; In methanol; at 0 - 20℃; for 16h; To a stirred solution of tert-butyl 4-(acetylthio)piperidine-1-carboxylate (8 g, 30.88 mmol, 1eq.) in methanol (80 mL) was added sodium borohydride (8.17 g, 21.62 mmol, 7 eq.) portion wise at 0 C. Reaction mixture was allowed to room temperature and stirred for 16 h. After complete conversion by TLC, reaction mixture was concentrated under reduced pressure. The residue was carefully dissolved in water and acidified with citric acid (pH = 6). The product was extracted with dichloromethane (2 X 100 mL), the extracts combined, dried over sodium sulfate, filtered and the filtrate evaporated in vacuum obtained the tert-butyl 4-mercaptopiperidine-1-carboxylate as a brown oil (6 g, 89%). TLC system: EtOAc/hexane (1:4), Rf value: ~ 0.4, KMnO4 stain+ve.1HNMR (400 MHz, DMSO-d6) δ 3.81-3.77 (m, 2H), 2.93-2.83 (m, 3H), 2.65 (d, J = 7.2 Hz, 1 H) 1.88-1.85 (m, 2H), 1.30-1.32 (m, 2H), 1.38 (s, 9H).
85% With methanol; sodium methoxide; at 0 - 20℃; for 5h; A solution of sodium methoxide (70 mL, 0.5 M in methanol, 35 mmol) was added dropwise to a stirring solution of tert-butyl 4-(acetylthio)piperidine-1- carboxylate (7.52 g, 29.0mmol) in methanol (120 mL) at 0 0C. The reaction was allowed to stir at O0C for 1 h and then warmed to room temperature and allowed to stir for an additional 4 h. The solvent was removed in vacuo and the residue was partitioned between ethyl acetate (150 mL) and water (150 mL). The organic layer was washed with water (2 x 100 mL), dried over sodium sulfate and concentrated in vacuo. Flash column chromatography (10% ethyl acetate:hexanes) afforded 5.35 g (85%) of the title compound as a pale yellow solid. 1H NMR (400 MHz, DMSO-ofe): δ 3.82-3.74 (m, 2H), 2.95- 2.75 (m, 3H), 2.64 (d, 1 H, J- 10 Hz), 1.89-1.81 (m, 2H), 1.42-1.27 (m, 2H), 1.37 (s, 9H).
68% With sodium methoxide; In methanol; at 0 - 20℃; for 5h; A methanol solution of sodium methoxide (1.1 g, 20 mmol) was added dropwise to a stirred solution of tert-butyl 4- (acetylthio)piperidine-l-carboxylate (4.2 g, 16 mmol) in 80 ml_ of anhydrous methanol at 0C. After 1 hour at 0C. The mixture was warmed to room temperature and then stirred for an additional 4 hours. The solvent was removed under reduced pressure and the residue was partitioned between EtOAc and water. The aqueous phase was extracted with EtOAc and the combined extracts were washed with brine, dried over sodium sulfate and concentrated. The residue was purified by flash chromatography (PE/EtOAc = 4: 1) to give tert-butyl 4-mercaptopiperidine-1-carboxylate (2.4 g, yield 68%). 1HNMR (400 MHz, DMSO-cfe): d 4.08-4.02 (m, 2H), 2.93-2.80 (m, 3H), 2.05- (0589) 1.96 (m, 2H), 1.90 (broad s, 1 H), 1.59-1.50 (m, 2H), 1.47 (s, 9H) ppm.
2.15 g 4-Acetylsulfanyl-piperidine-1-carboxylic acid tert-butyl ester (272) were dissolved in 84 ml MeOH and treated with 2.1 g (55.5 mmol) sodium borohydride at O0C. after stirring for 2 h at RT all volatiles were removed in vacuo and to the residue was added slowly water and 2.3 g (11 mmol) citric acid monohydrate. Extraction with dichloromethane, drying with Sodium sulfate and evaporation gave 1.78 g of crude 4- Mercapto-piperidine-1-carboxylic acid tert-butyl ester
With water monomer; sodium hydroxide; In methanol; for 2h; Step B - Synthesis of Compound 13B To a solution of Compound 13A (0.50 g, 1.9 mmol) in MeOH (6 ml) was added 1.0N NaOH (2.9 rnL). The resulting reaction was allowed to stir 2 hours, then 1.0N HCl (2.9 mL) was added and the resulting solution was concentrated in vacuo. The residue obtained was taken up in EtOH (15 mL) and filtered and the filtrate was concentrated in vacuo to provide Compound 13B as a brown oil, which was used without further purification.
With sodium methoxide; In methanol; at 0 - 20℃; for 5h; [0141] A solution of sodium methoxide (prepared from 570 mg of sodium in 20 mL of anhydrous methanol, 25 mmol)was added dropwise to a stirred solution of tert-butyl 4-(acetylsulfanyl)piperidine-1-carboxylate (5.2 g, 21 mmol) in 80mL of anhydrous methanol at 0 C. After 1 h at 0 C for the mixture was allowed to warm to room temperature and thenstirred for an additional 4 h. The solvent was removed in vacuo and the residue was partitioned between EtOAc andwater. The aqueous phase was extracted with EtOAc and the combined extracts were washed with brine, dried oversodium sulfate and concentrated. The residue was purified by flash chromatography (Petrol ether/EtOAc = 4:1) to providetert-butyl 4-sulfanylpiperidine-1-carboxylate. 1H-NMR (400 MHz, CDCl3) δ ppm 4.83 (m, 1H), 3.93∼3.97 (m, 2H),2.71∼2.82 (m, 3H), 1.90∼1.93 (m, 2H), 1.43∼1.50 (m, 2H), 1.39 (s, 9H).

  • 3
  • [ 54288-70-9 ]
  • [ 141699-66-3 ]
 

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