Structure of 181646-38-8
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CAS No. : | 181646-38-8 |
Formula : | C10H19NO3 |
M.W : | 201.26 |
SMILES Code : | O=C(OC(C)(C)C)NC(CC=O)(C)C |
MDL No. : | MFCD24465551 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With sulfur trioxide pyridine complex; dimethyl sulfoxide; triethylamine; at 25℃; for 1h; | <strong>[167216-22-0](3-Hydroxy-1,1-dimethyl-propyl)-carbamic acid tert-butyl ester</strong> (9.8 g, 0.048 mol) was dissolved in DMSO (160 mL). The solution was treated with Et3N (20.2 mL, 0.145 mol) followed by a solution of pyridine sufurtrioxide complex (23.2 g, 0.145 mol) in DMSO (160 mL). Upon complete addition, the solution was stirred for 1 h at 25 C. The mixture was diluted with brine and extracted with Et2O (3 x 125 mL). The organic phase was washed with 10% citric acid (aq), saturated NaHCO3 and brine. The organic phase was dried (MgSO4) and concentrated to the desired material as a yellow oil (8. 3 g, 56%): 1H NMR (DMSO-d6) δ 9.67 (t, 1H, J = 3 Hz), 2.66 (s, 2H), 1.37 (s, 9H), 1.28 (s, 6H). |
With pyridine; triethylamine; In dimethyl sulfoxide; | Step 5: (1,1-Dimethyl-3-oxo-propyl)-carbamic acid tert-butyl ester. <strong>[167216-22-0](3-Hydroxy-1,1-dimethyl-propyl)-carbamic acid tert-butyl ester</strong>(9.8 g, 0.048 mol)was dissolved in DMSO(160 mL). The solution was treated with Et3N(20.2 mL, 0.145 mol) followed by a solution of pyridine sufurtrioxide complex(23.15 g, 0.145 mol) in DMSO(160 mL). Upon complete addition, the solution was stirred for 1 h at 25 C. The mixture was diluted with brine and extracted with Et2O(3*125 mL). The organic phase was washed with 10% citric acid(aq), saturated NaHCO3 and brine. The organic was dried(MgSO4) and concentrated to the desired material as a yellow oil(8.3 g, 56%); 1H NMR (DMSO-d6) δ 9.67 (t, J=3 Hz, 1H), δ 2.66 (s, 2H), δ 1.37 (s, 9H), δ 1.28 (s, 6H). | |
With hydrogenchloride; oxalyl dichloride; dimethyl sulfoxide; triethylamine; In n-heptane; dichloromethane; ethyl acetate; at -78℃; for 0.583333h; | 3-(tert-Butoxycarbonylamino)-3-methylbutanal At -78 C. DMSO (1.22 ml, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 ml, 12.9 mmol) in dichloromethane (15 ml).. The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 ml) was added dropwise over a period of 15 min.. The solution was stirred at -78 C. for another 15 min.. triethylamine (6.0 ml, 43 mmol) was added.. The solution was stirred at -78 C. for 5 min and then warmed to room temp.. The solution was diluted with dichloromethane (100 ml) and extracted with 1N hydrochloric acid (100 ml).. The aqueous phase was extracted with dichloromethane (50 ml).. The combined organic layers were washed with a saturated solution of sodium hydrogencarbonate (100 ml) and dried over magnesium sulfate.. The solvent was removed in vacuo.. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. 400 MHz-1H-NMR (CDCl3): d=1.39 (s, 6 H); 1.45 (s, 9 H); 2.85 (d, 2 H); 4.73 (br. 1 H); 9.80 (t, 1 H). |
With pyridine-SO3 complex; triethylamine; In dimethyl sulfoxide; at 20℃; for 72h; | Step 2: tert-butyl (3-amino-1,1-dimethyl-propyl)-carbamate; 38.6 g (242.7 mmol) sulphur trioxide-pyridine complex are added at ambient temperature to 31.9 g (157 mmol) tert-butyl (3-amino-1,1-dimethyl-propyl)-carbamate and 63.3 mL (455 mmol) triethylamine in 400 mL dimethylsulphoxide. The reaction mixture is stirred for 72 hours at ambient temperature and then combined with 200 mL toluene and 300 mL water. The phases are separated and the aqueous phase is extracted with toluene. The combined organic phases are washed successively with aqueous potassium hydrogen sulphate solution (0.5 M), aqueous sodium hydrogen carbonate solution (10% ish) and water, dried on sodium sulphate and concentrated by evaporation in the rotary evaporator. | |
1.8 g | With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 3h; | To a solution of the <strong>[167216-22-0]tert-butyl (4-hydroxy-2-methylbutan-2-yl)carbamate</strong> (2 g, 9.8 mmol) in DCM (18 mL) at 0C was added Dess-Martin periodinane (7.2 g, 17.14 mmol). The reactionmixture was stirred at RT for 3 h. Progress of reaction was monitored TLC. After completion, reaction mixture was quenched with aq. NaHCO3, and extracted with EtOAc (2 x 50 mL). Combined organic layer was washed with brine (2 x 20 mL), dried over sodium sulfate. Removal of solvent gave crude which was purified by silica gel column chromatography using ethyl acetate-hexane as eluent to afford tert-butyl (2-methyl-4-oxobutan-2-yl)carbamate as a yellowsolid (1.8 g). |
1.8 g | With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 3h; | To a solution of the <strong>[167216-22-0]tert-butyl (4-hydroxy-2-methylbutan-2-yl)carbamate</strong> (2 g, 9.8 mmol) in DCM (18 mL) at 0 C. was added Dess-Martin periodinane (7.2 g, 17.14 mmol). The reaction mixture was stirred at RT for 3 h. Progress of reaction was monitored TLC. After completion, reaction mixture was quenched with aq. NaHCO3, and extracted with EtOAc (2*50 mL). Combined organic layer was washed with brine (2*20 mL), dried over sodium sulfate. Removal of solvent gave crude which was purified by silica gel column chromatography using ethyl acetate-hexane as eluent to afford tert-butyl (2-methyl-4-oxobutan-2-yl)carbamate as a yellow solid (1.8 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydrogencarbonate; sodium thiosulfate; In dichloromethane; water; | PREPARATION 102 (1,1-Dimethyl-3-oxo-propyl)-carbamic acid tert-butyl ester <strong>[167216-22-0](3-Hydroxy-1,1-dimethyl-propyl)-carbamic acid tert-butyl ester</strong> (6.0 g, 30 mmol) was dissolved in CH2Cl2 (50 mL) and treated with Dess-Martin periodinane (20.0 g, 44 mmol). After stirring overnight 50 mL of water was added followed by NaHCO3 and Na2S2O3. The resultant mixture was stirred vigorously for 30 min and then was extracted with CH2Cl2 (3-50 mL). The extracts were dried with MgSO4 and concentrated to give 3.26 9 (54%) of an orange oil. This material was used in the next step without purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In n-heptane; dichloromethane; dimethyl sulfoxide; | 3-(tert-Butoxycarbonylamino)-3-methylbutanal: DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (15 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. MHz-1H-NMR (CDCl3): δ1.39 (s, 6 H); 1.45 (s, 9 H); 2.85 (d, 2 H); 4.73 (br. 1 H); 9.80 (t, 1 H). | |
With sodium hydrogencarbonate; triethylamine; In n-heptane; dichloromethane; dimethyl sulfoxide; | 3-(tert-Butoxycarbonylamino)-3-methylbutanal STR83 At -78 C. DMSO (1.22 ml, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 ml, 12.9 mmol) in dichloromethane (15 ml). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 ml) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 ml, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temp. The solution was diluted with dichloromethane (100 ml) and extracted with 1N hydrochloric acid (100 ml). The aqueous phase was extracted with dichloromethane (50 ml). The combined organic layers were washed with a saturated solution of sodium hydrogencarbonate (100 ml) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. 400 MHz-1H-NMR (CDCl3): d=1.39 (s, 6H); 1.45 (s, 9H); 2.85 (d, 2H); 4.73 (br. 1H); 9.80 (t, 1H). | |
With triethylamine; In n-heptane; dichloromethane; dimethyl sulfoxide; | Step B 3-(tert-Butoxycarbonylamino)-3-methylbutanal DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (15 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. MHz-1H-NMR (CDCl3): d 1.39 (s, 6 H); 1.45 (s, 9 H); 2.85 (d, 2 H); 4.73 (br. 1 H); 9.80 (t, 1 H). |
With triethylamine; In n-heptane; dichloromethane; dimethyl sulfoxide; | Step B 3-(tert-Butoxycarbonylamino)-3-methylbutanal DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (15 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. | |
With triethylamine; In n-heptane; dichloromethane; dimethyl sulfoxide; | DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (I 5 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1 N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. MHz-1H-NMR (CDCl3): d 1.39 (s, 6H); 1.45 (s, 9H); 2.85 (d, 2H); 4.73 (br, 1H); 9.80 (t, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; | Step B: DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (15 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1 N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. 1 H-NMR (CDCl3): d 1.39 (s, 6H); 1.45 (s, 9H); 2.85 (d, 2H); 4.73 (br. 1H); 9.80 (t, 1H). | |
With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; | Step B: DMSO (1.22 mL, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 mL, 12.9 mmol) at -78 C. in dichloromethane (15 mL). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 mL) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 mL, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 mL) and extracted with 1N hydrochloric acid (100 mL). The aqueous phase was extracted with dichloromethane (50 mL). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 mL) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. MHz-1 H-NMR (CDCl3): d 1.39 (s, 6 H); 1.45 (s, 9 H); 2.85 (d, 2 H); 4.73 (br. 1H); 9.80 (t, 1 H). | |
With oxalyl dichloride; dimethyl sulfoxide; triethylamine; In dichloromethane; | 3-(tert-Butoxycarbonylamino)-3-methylbutanal: STR105 Dimethylsufoxide (1.22 ml, 17.2 mmol) was added to a solution of oxalyl chloride (1.1 ml, 12.9 mmol) at -78 C. in dichloromethane (15 ml). The mixture was stirred for 15 min at -78 C. A solution of 3-hydroxy-1,1-dimethylpropylcarbamic acid tert-butyl ester (1.75 g, 8.6 mmol) in dichloromethane (10 ml) was added dropwise over a period of 15 min. The solution was stirred at -78 C. for another 15 min. Triethylamine (6.0 ml, 43 mmol) was added. The solution was stirred at -78 C. for 5 min and then warmed to room temperature. The solution was diluted with dichloromethane (100 ml) and extracted with 1N hydrochloric acid (100 ml). The aqueous phase was extracted with dichloromethane (50 ml). The combined organic layers were washed with saturated sodium hydrogen carbonate solution (100 ml) and dried over magnesium sulfate. The solvent was removed in vacuo. The crude product was purified by column chromatography on silica (140 g) with ethyl acetate/heptane (1:3) to give 1.10 g of 3-(tert-butoxycarbonylamino)-3-methylbutanal. 1 H-NMR (CDCl3):-- d 1.39 (s, 6 H); 1.45 (s, 9 H); 2.85 (d, 2 H); 4.73 (br. 1 H); 9.80 (t, 1 H). |