Pyridine → HCID 58994328, compound

HRID 1508154Notes

Reaction equation

HRID 1508154 reaction equation
[C:1]([C:3]1[N:4]=[C:5]([C:16]([O-:18])=O)[N:6]([CH2:8][O:9][CH2:10][CH2:11][Si:12]([CH3:15])([CH3:14])[CH3:13])[CH:7]=1)#[N:2].[K+].N1C=CC=CC=1.O=S(Cl)Cl.[C:30]([Si:34]([CH3:56])([CH3:55])[O:35][CH2:36][C:37]([C:40]1[CH:45]=[CH:44][C:43]([NH2:46])=[C:42]([C:47]2[CH2:52][CH2:51][C:50]([CH3:54])([CH3:53])[CH2:49][CH:48]=2)[CH:41]=1)([CH3:39])[CH3:38])([CH3:33])([CH3:32])[CH3:31]>C(Cl)Cl.CCOC(C)=O>[C:30]([Si:34]([CH3:55])([CH3:56])[O:35][CH2:36][C:37]([C:40]1[CH:45]=[CH:44][C:43]([NH:46][C:16]([C:5]2[N:6]([CH2:8][O:9][CH2:10][CH2:11][Si:12]([CH3:13])([CH3:14])[CH3:15])[CH:7]=[C:3]([C:1]#[N:2])[N:4]=2)=[O:18])=[C:42]([C:47]2[CH2:52][CH2:51][C:50]([CH3:54])([CH3:53])[CH2:49][CH:48]=2)[CH:41]=1)([CH3:39])[CH3:38])([CH3:33])([CH3:31])[CH3:32]

Participants

7

Reactant 4

HCID 1049PyridineHCID 24386Thionyl ChlorideHCID 58994480HCID 58994480, compoundHCID 67188357potassium 4-cyano-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazole-2-carboxylate

Product 1

HCID 58994328HCID 58994328, compoundYield 93%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of potassium 4-cyano-1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole-2-carboxylate (as prepared in Example 1, step (d), 1.37 g, 4.49 mmol) and pyridine (363 μL, 4.49 mmol) in 15 mL of DCM at 0° C. was added SOCl2 (328 μL, 4.49 mmol). After stirring at 0° C. for 0.5 h under Ar, the resulting mixture was warmed to RT and added to a solution of 4-[2-(tert-butyl-dimethyl-silanyloxy)-1,1-dimethyl-ethyl]-2-(4,4-dimethyl-cyclohex-1-enyl)-phenylamine (as prepared in the previous step, 1.45 g, 3.74 mmol) in 15 mL of DCM at 0° C. After stirring at 0° C. for 2 h under Ar, the reaction was warmed to RT. Treated with 100 mL of EtOAc, the mixture was washed with H2O (20 mL), 10% aqueous citric acid (20 mL), aqueous saturated NaHCO3 (20 mL) and brine (20 mL). The organic layer was dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel chromatography (0-5% EtOAc/hexane) to afford the title compound (2.22 g, 93%) as a light brown oil. Mass spectrum (ESI, m/z): Calcd. for C35H56N4O3Si2, 637.4 (M+H). found 637.2.

Workup

  1. temperaturethe resulting mixture was warmed to RT
  2. stirringAfter stirring at 0° C. for 2 h under Ar
  3. temperaturethe reaction was warmed to RT
  4. washthe mixture was washed with H2O (20 mL), 10% aqueous citric acid (20 mL), aqueous saturated NaHCO3 (20 mL) and brine (20 mL)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography (0-5% EtOAc/hexane)

Sources & evidence

ORD record
ord-844eb691a50045ddaa146dd322c3492a
Source dataset
uspto-grants-2015_12
Patent number
US09221797B2

Reaction notes

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