Methanol → (R)-(+)-4-tert. butoxy-3-methylbutyronitrile

HRID 1701248Notes

Reaction equation

HRID 1701248 reaction equation
[C:1]([O:5][CH2:6][C@H:7]([CH3:10])[CH2:8]Br)([CH3:4])([CH3:3])[CH3:2].BrOBr.[C-:14]#[N:15].[Na+].CO>O>[C:1]([O:5][CH2:6][C@H:7]([CH3:10])[CH2:8][C:14]#[N:15])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 887MethanolHCID 8929Sodium CyanideHCID 86735108bromo ether (S)-(+)-3-tert. butoxy-2-methyl-1-bromopropane

Product 1

HCID 12923321(R)-(+)-4-tert. butoxy-3-methylbutyronitrileYield 64.6%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A mixture of 23.1 g. (0.11 mole) of bromo ether (S)-(+)-3-tert. butoxy-2-methyl-1-bromopropane and 11.07 g. (0.225 mole) of sodium cyanide in 144 ml. of methanol and 36 ml. of water was stirred and refluxed for 17 hours. After cooling, the reaction mixture was diluted with water and worked up by extraction with CH2Cl2 in the manner of Example 1. The crude product was chromatographed on 500 g. of silica gel. Elution with 9:1 parts by volume and 4:1 parts by volume hexane-ether followed by evaporative distillation gave (R)-(+)-4-tert. butoxy-3-methylbutyronitrile (11.03 g.; 64.5%) as a colorless liquid, b.p. 88°-90° C. (bath temperature) (11 mm Hg.); [α]25D+7.41° (c 1.8, C6H6).

Workup

  1. additionA mixture of 23.1 g
  2. temperaturerefluxed for 17 hours
  3. temperatureAfter cooling
  4. extractionworked up by extraction with CH2Cl2 in the manner of Example 1
  5. customThe crude product was chromatographed on 500 g
  6. washElution with 9:1 parts by volume and 4:1 parts by volume hexane-ether
  7. distillationfollowed by evaporative distillation

Sources & evidence

ORD record
ord-f21dd835ad024c0ca347348c9f23ba6c
Source dataset
uspto-grants-1980_03
Patent number
US04191842

Reaction notes

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