tert-Butyldimethylsilyl chloride → 4,4-Dimethyl-5-t-butyldimethylsilyloxyvaleronitrile

HRID 330613Notes

Reaction equation

HRID 330613 reaction equation
[CH3:1][C:2]([CH3:9])([CH2:7][OH:8])[CH2:3][CH2:4][C:5]#[N:6].C(N(C(C)C)CC)(C)C.[Si:19](Cl)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20]>C(Cl)Cl.CN(C)C1C=CN=CC=1>[CH3:1][C:2]([CH3:9])([CH2:7][O:8][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])[CH2:3][CH2:4][C:5]#[N:6]

Participants

6

Reactant 3

HCID 28928tert-Butyldimethylsilyl chlorideHCID 81531DiisopropylethylamineHCID 913575-Hydroxy-4,4-dimethylvaleronitrile

Product 1

HCID 147501114,4-Dimethyl-5-t-butyldimethylsilyloxyvaleronitrileYield 69%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

To a solution of 16.13 g (0.127 mmol) of 4,4-dimethyl-5-hydroxyvaleronitrile in 250 mL of dry CH2Cl2 was added, at 20° C., in 2 min., 24.2 mL (0.139 mmol; 1.09 eq) of diisopropylethylamine, followed after 5 min. by 25.0 g (0.165 mmol; 1.3 eq) of solid t-butyldimethylsilyl chloride, all at once. Then, 1.55 g (0.0127 mmol; 0.1 eq) of 4-dimethylaminopyridine was added and the whole was stirred at 20° C. during 18h. After removing the solvent under vacuum (aspirator) the brown residue was taken up in H2O, followed by ethyl ether. The layers were separated and the aqueous one extracted three times with 200 mL of ether. The combined organic layers were back extracted with water (100 mL), HCl 1.2N (100 mL), 5% KHCO3 (2×100 mL), dried over Na2SO4 and concentrated under vacuum to give a faint yellow oil. Distillation at 94°-97° C. (0.7 mm) gave 21 g (69%) of the title compound. TLC:(Silica),Rf 0.59(CH2Cl2), detection with molybdophosphoric acid blue on yellow.

Workup

  1. customAfter removing the solvent under vacuum (aspirator) the brown residue
  2. customThe layers were separated
  3. extractionthe aqueous one extracted three times with 200 mL of ether
  4. extractionThe combined organic layers were back extracted with water (100 mL), HCl 1.2N (100 mL), 5% KHCO3 (2×100 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under vacuum
  7. customto give a faint yellow oil
  8. distillationDistillation at 94°-97° C. (0.7 mm)

Sources & evidence

ORD record
ord-caefd070b9124374b25c784f7d452080
Source dataset
uspto-grants-1990_01
Patent number
US04897477

Reaction notes

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