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Structure of 90101-22-7

Chemical Structure| 90101-22-7

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Product Details of [ 90101-22-7 ]

CAS No. :90101-22-7
Formula : C11H16N2O2
M.W : 208.26
SMILES Code : O=C(OC(C)(C)C)NC1=NC(C)=CC=C1
MDL No. :MFCD07776935
InChI Key :XSVAARVWQDEAEL-UHFFFAOYSA-N
Pubchem ID :11367776

Safety of [ 90101-22-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H317
Precautionary Statements:P280

Application In Synthesis of [ 90101-22-7 ]

* 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 [ 90101-22-7 ]

[ 90101-22-7 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 90101-22-7 ]
  • [ 74-88-4 ]
  • [ 205676-84-2 ]
YieldReaction ConditionsOperation in experiment
78% With NaH; In water; dimethyl sulfoxide; mineral oil; b) 2-[(tert-Butoxycarbonyl)methylamino]-6-picoline NaH (60% in mineral oil, 3.60 g, 90 mmole) was added in portions over several min to a solution of 2-(tert-butoxycarbonylamino)-6-picoline (15.62 g, 75 mmole) and iodomethane (9.3 mL, 150 mmole) in anhydrous DMSO (75 mL) at 15 C. (cool water bath). The internal temperature rose to 35 C. When gas evolution had subsided, the cool water bath was removed and the reaction was allowed to stir at RT. After 0.5 hr, the dark yellow mixture was poured onto ice/H2O (300 mL) and extracted with Et2O (3*300 mL). The combined organic layers were washed sequentially with H2O (2*75 mL) and brine (75 mL). Drying (MgSO4) and concentration left a yellow oil which was chromatographed on silica gel (7% EtOAc/hexanes). The title compound (13.01 g, 78%) was obtained as a faintly yellow oil: 1H NMR (250 MHz, CDCl3) δ7.51 (app t, 1 H), 7.37 (d, J=8.2 Hz, 1 H), 6.86 (d, J=7.2 Hz, 1 H), 3.38 (s, 3 H), 2.49 (s, 3 H), 1.50 (s, 9 H); MS (ES) m/e 223 (M+H)+.
74% Step BSodium hydride (0.84 g, 35 mmol) was suspended in N,N'-dimethylformamide (50 mL) and the mixture was cooled to 0 C. At 0 C. a solution of the title compound from Step A above (6 g, 28.8 mmol) in N,N'-dimethylformamide (20 mL) was added over a period of 5 minutes. After the addition was completed, the reaction mixture was stirred at 0 C. for 15 minutes and then 60 minutes at room temperature. Then methyliodide (2.39 mL, 38.5 mmol) was added in one portion and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate (150 mL) and 10% citric acid solution (150 mL). The organic phase was separated and the aqueous phase was extracted with ethylacetate (2×100 mL). The combined organic phase was washed with 10% citric acid solution (80 mL), saturated sodium bicarbonate (80 mL) and brine (80 mL). The organic phase was separated, dried over Na2SO4, filtered and the solvents were removed. The residue was purified by chromatography on silica using ethyl acetate/petrolether (10/90) to afford the desired compound as a pale yellow oil (4.75 g, 74%).1H-NMR (400 MHz, CDCl3): δ=1.53 (s, 9H), 2.48 (s, 3H), 3.38 (s, 3H), 6.87 (d, 1H), 7.40 (d, 1H), 7.52 (t, 1H)
74% Step B ; Sodium hydride (0.84 g, 35 mmol) was suspended in N,N'-dimethylformamide (50 mL) and the mixture was cooled to 0 C. At 0 C a solution of the title compound from Step A above (6 g, 28.8 mnol) in N,N'-dimethylformamide (20 mL) was added over a period of 5 minutes. After the addition was completed, the reaction mixture was stirred at 0 C for 15 minutes and then 60 minutes at room temperature. Then methyliodide (2.39 mL, 38.5 mmol) was added in one portion and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate (150 mL) and 10 % citric acid solution (150 mL). The organic phase was separated and the aqueous phase was extracted with ethylacetate (2 x 100 mL). The combined organic phase was washed with 10 % citric acid solution (80 mL), saturated sodium bicarbonate (80 mL) and brine (80 mL). The organic phase was separated, dried over Na2SO4, filtered and the solvents were removed. The residue was purified by chromatography on silica using ethyl acetate/petrolether (10/90) to afford the desired compound as a pale yellow oil (4.75 g, 74 %). 1H-NMR (400 MHz, CDCl3): d = 1.53 (s, 9H), 2.48 (s, 3H), 3.38 (s, 3H), 6.87 (d, 1H), 7.40 (d, 1H), 7.52 (t, 1H)
74% Sodium hydride (0.84 g, 35 mmol) was suspended in N,N'-dimethylfonnamide (50 mL) and the mixture was cooled to 0 C . At 0 C a solution of the title compound from Step A above (6 g, 28.8 mmol) in Ν,Ν'-dimethylformamide (20 mL) was added over a period of 5 minutes. After the addition was completed, the reaction mixture was stirred at 0 C for 15 minutes and then 60 minutes at room temperature. Then methyliodide (2.39 mL, 38.5 mmol) was added in one portion and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate ( 150 mL) and 10 % citric acid solution ( 150 mL). The organic phase was separated and the aqueous phase was extracted with ethylacetate (2 x 100 mL). The combined organic phase was washed with 10 % citric acid solution (80 mL), saturated sodium bicarbonate (80 mL) and brine (80 mL). The organic phase was separated, dried over Na2S04, filtered and the solvents were removed. The residue was purified by chromatography on silica using ethyl acetate/petrolether (10/90) to afford the desired compound as a pale yellow oil (4.75 g, 74 %).1H- MR (400 MHz, CDC13): d = 1,53 (s, 9H), 2.48 (s, 3H), 3.38 (s, 3H), 6.87 (d, 1 H), 7.40 (d, 1 H), 7.52 (t, 1H)
74% Sodium hydride (0.84 g, 35 mmol) was suspended in N,N’-dimethylformamide (50 mL) and the mixture cooled to 0C. At 0C a solution of starting material1, (6 g, 28.8 mmol), prepared as described1, in N,N’-dimethylformamide (20 mL) was added over a period of 5 minutes. After the addition was completed, the reaction mixture was stirred at 0C for 15 minutes and then 60 minutes at room temperature. Then methyliodide (2.39 ml, 38.5 mmol) was added in one portion and the reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate (150 mL) and 10 % citric acid solution (150 mL). The organic phase was separated and the aqueous phase extracted with ethyl acetate (2 x 100 mL). The combined organic phase was washed with 10 % citric acid solution (80 mL), saturated sodium bicarbonate (80 mL)and brine (80 mL). The organic phase was separated, dried over Na2SO4,filtered and the solvents removed. The residue was purified by chromatography on silica using ethyl acetate/petrol ether (10/90) to afford the desired compound as a pale yellow oil (4.75 g, 74 %).1H-NMR (400 MHz, CDCl3):δ = 1.53 (s, 9H), 2.48 (s, 3H), 3.38 (s, 3H), 6.87 (d, 1H), 7.40 (d, 1H), 7.52 (t, 1H)
With NaH; In N,N-dimethyl-formamide; mineral oil; b 2-[(tert-Butoxycarbonyl)methylamino]-6-picoline To the suspension of NaH (60% dispersion in mineral oil, 0.44 g, 11 mmol) in DMF (20 mL) at 0 C. was added a solution of 2-(tert-butoxycarbonylamino)-6-picoline (2.1 g,10 mmol) in DMF (30 mL). The reaction was stirred at 0 C. for 15 min; then methyl iodide (1.6 g, 11 mmol) was added. The reaction mixture was concentrated in vacuum, diluted with H2O, and extracted with CH2Cl2 (3*50 mL). Drying (MgSO4) and concentration gave the title compound as a colorless oil.
A 1 L round bottom flask was charged with THF (200 mL) and sodium hydride (60% in mineral oil, 22 g, 0.55 mol). A solution of 2-(tert)-butoxycarbonylamino)-6-picoline (100 g, 99.2% PAR, 0.48 mol) in THF (200 mL) was added over 45 minutes while maintaining temperature 20 ~ 25 C. The resulting mixture was stirred for 15 minutes followed by addition OF IODOMETHANE (102 mL, 1.64 mol) over 1 h, while maintaining temperature 20- 25 C. The resulting mixture was stirred for 3 h at room temperature. Deionized H20 (100 ML) was added and the two layers separated. The aqueous layer was extracted with hexane (150 mL). The combined organic layers were washed with deionized H20 (2 x 100 mL) and concentrated to provide the title product (107.6 g).
With sodium hydride; In dimethyl sulfoxide; at 15 - 35℃; for 0.5h; NaH (60% in mineral oil, 3.60 g, 90 mmole) was added in portions over several min to a solution of 2-(tert-butoxycarbonylamino)-6-picoline (15.62 g, 75 mmole) and iodomethane (9.3 mL, 150 mmole) in anhydrous DMSO (75 mL) at 15 C (cool water bath). The internal temperature rose to 35 C. When gas evolution had subsided, the cool water bath was removed and the reaction was allowed to stir at RT. After 0.5 hr, the dark yellow mixture was poured onto ice/H2O (300 mL) and extracted with Et2O (3 × 300 mL). The combined organic layers were washed sequentially with H2O (2 × 75 mL) and brine (75 mL). Drying (MgSO4) and concentration left a yellow oil which was chromatographed on silica gel (7% EtOAc/hexanes). The title compound (13.01 g, 78%) was obtained as a faintly yellow oil: 1H NMR (250 MHz, CDCl3) δ 7.51 (app t, 1 H), 7.37 (d, J = 8.2 Hz, 1 H), 6.86 (d, J = 7.2 Hz, 1 H), 3.38 (s, 3 H), 2.49 (s, 3 H), 1.50 (s, 9 H); MS (ES) m/e 223 (M + H)+.

 

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