Water → 4-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-butanenitrile

HRID 75177Notes

Reaction equation

HRID 75177 reaction equation
CS(O[CH:6]([CH2:16][CH2:17][O:18][Si:19]([CH3:25])([CH3:24])[C:20]([CH3:23])([CH3:22])[CH3:21])[CH2:7][O:8][Si:9]([CH3:15])([CH3:14])[C:10]([CH3:13])([CH3:12])[CH3:11])(=O)=O.[C-:26]#[N:27].[Na+].O>CS(C)=O>[CH3:23][C:20]([Si:19]([CH3:24])([CH3:25])[O:18][CH2:17][CH2:16][CH:6]([CH2:7][O:8][Si:9]([C:10]([CH3:11])([CH3:12])[CH3:13])([CH3:14])[CH3:15])[C:26]#[N:27])([CH3:21])[CH3:22]

Participants

5

Reactant 3

HCID 962WaterHCID 8929Sodium CyanideHCID 86674468HCID 86674468, compound2×

Product 1

HCID 232517064-[[(1,1-Dimethylethyl)dimethylsilyl]oxy]-2-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-butanenitrile

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 6-methylsulfonyloxy-2,2,3,3,10,10,11,11-octamethyl-4,9-dioxa-3,10-disiladodecane (i.e. the product of Step B) (59.29 g, 0.144 mol) and sodium cyanide (15.55 g, 0.317 mol) in DMSO was heated at 90° C. (using an oil bath) for 2 h. The reaction mixture was cooled to room temperature, water (500 mL) was added and the mixture was extracted with diethyl ether (4×250 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (300 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure to a dark-yellow oil (48.86 g). The oil was purified by silica gel chromatography (eluting with petroleum ether, followed 1-4% gradient of ethyl acetate in petroleum ether) to provide the title compound (150 mg), a compound of the present invention, as a dark foam. Mixed fractions were combined with mixtures from a previous experiment (total weight 19 g) and purified by silica gel chromatography to provide the title compound (about 11 g).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionthe mixture was extracted with diethyl ether (4×250 mL)
  3. washThe combined organic layers were washed with saturated aqueous sodium chloride solution (300 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure to a dark-yellow oil (48.86 g)
  7. customThe oil was purified by silica gel chromatography (eluting with petroleum ether, followed 1-4% gradient of ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-c18572ac5f974508ac638eb30f917766
Source dataset
uspto-grants-2014_09
Patent number
US08835427B2

Reaction notes

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