Dichloromethane → HCID 18779722, compound

HRID 1421765Notes

Reaction equation

HRID 1421765 reaction equation
C([SiH2]O[C:7]([CH3:16])(C)[C:8]1[CH2:9][N:10](O)[CH:11]=[CH:12][CH:13]=1)(C)(C)C.C[Si]([C:21]#[N:22])(C)C.C[N:24]([CH3:28])[C:25](Cl)=O.[C:29]([O-:32])(O)=O.[Na+].C([SiH2]OC(C)(C)[C:41]1[C:42]([C:47]#[N:48])=[N:43][CH:44]=[CH:45][CH:46]=1)(C)(C)C.C([SiH2]O[C:57]([CH3:67])(C)[C:58]1C=CC(C#N)=[N:62][CH:63]=1)(C)(C)C.C(Cl)[Cl:69]>>[Cl:69][C:58]1[CH:57]=[CH:67][C:29](=[O:32])[N:62]([C:11]2[CH:12]=[CH:13][C:8]([CH2:7][C:16]3[N:24]([CH2:28][C:45]4[CH:46]=[CH:41][C:42]([C:47]#[N:48])=[N:43][CH:44]=4)[CH:25]=[N:22][CH:21]=3)=[CH:9][N:10]=2)[CH:63]=1

Participants

8

Reactant 7

HCID 6344DichloromethaneHCID 6598Dimethylcarbamoyl Chloride2×HCID 82115Trimethylsilyl cyanide2×HCID 516892Sodium BicarbonateHCID 131721348HCID 131721348, compoundHCID 137328803HCID 137328803, compoundHCID 178455431HCID 178455431, compound

Product 1

HCID 18779722HCID 18779722, compound

Procedure

3-(tert-Butyl-dimethyl-silanyloxymethyl)-pyridin-1-ol from step 1 (2.4 g, 9.9 mmol) was dissolved in CH2Cl2 (100 mL) and treated with trimethylsilylcyanide (1.3 ml, 9.9 mmol). The reaction mixture was stirred for 5 min. at room temperature. The mixture was then treated with dimethylcarbamyl chloride (910 μl, 9.9 mmol) and stirred at room temperature for 15 hours. HPLC analysis showed that the reaction had not gone to completion. More trimethylsilylcyanide (264 μl, 1.98 mmol) and dimethylcarbamyl chloride (910 μl, 9.9 mmol) were added and the reaction mixture was heated to 75° C. for 3.5 hrs. The reaction was cooled to room temperature and saturated NaHCO3 (50 mL) was added. The mixture was separated and the water layer was extracted with CH2Cl2 (2×40 mL). The combined organic layers were dried (MgSO4), filtered, and concentrated. The residue was purified by flash chromatography [2% MeOH(5% NH4OH)/CH2Cl2) to yield a mixture of of 3-(tert-Butyl-dimethyl-silanyloxymethyl)-pyridine-2-carbonitrile and 5-(tert-Butyl-dimethyl-silanyloxymethyl)-pyridine-2-carbonitrile (10:1).

Workup

  1. stirringstirred at room temperature for 15 hours
  2. temperaturethe reaction mixture was heated to 75° C. for 3.5 hrs
  3. temperatureThe reaction was cooled to room temperature
  4. customThe mixture was separated
  5. extractionthe water layer was extracted with CH2Cl2 (2×40 mL)
  6. dry with materialThe combined organic layers were dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography [2% MeOH(5% NH4OH)/CH2Cl2)
  10. customto yield

Sources & evidence

ORD record
ord-dee3b37276de4b218ef5b05765b27e15
Source dataset
uspto-grants-2000_06
Patent number
US06077853

Reaction notes

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