Hydrochloric Acid → 3-Hydroxy-4-methyl-2-methylenepentanenitrile

HRID 2181391Notes

Reaction equation

[N:1]12[CH2:8][CH2:7]N(CC1)CC2.[CH:9](=[O:13])[CH:10]([CH3:12])[CH3:11].[C:14](#N)C=C.Cl>C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.O>[OH:13][CH:9]([CH:10]([CH3:12])[CH3:11])[C:7](=[CH2:14])[C:8]#[N:1]

Participants

Conditions

Temperature: 25 °C

Procedure

A 250 mL, three-necked, round-bottom flask with overhead stirring is charged with 0.36 g (1.6 mmol) of 2,6-di-tert-butyl-4-methylphenol, 37 g (0.33 mol) of 1,4-diazabicyclo[2,2,2]octane, 60 mL (0.66 mol) of isobutyraldehyde, 52 mL (0.79 mol) of acrylonitrile, and 7.2 mL (0.4 mol) of water. The reaction mixture is stirred at 50° C. for 24 hours, cooled to 25° C., and quenched into a solution of 33 mL (0.38 mol) of hydrochloric acid and 100 mL of water. The product is extracted with 120 mL of methylene chloride. The aqueous acid layer is extracted again with 25 mL of methylene chloride. The combined methylene chloride layers are concentrated by rotary evaporation to provide 79.9 g (96.7%) of 3-hydroxy-4-methyl-2-methylenepentanenitrile as a yellow oil (which may solidify to a white solid on standing), 96.7% (area under the curve) by HPLC assay, which may be used in the next step without further purification. Carbonic acid 2-cyano-1-isopropyl-allyl ester ethyl ester

Workup

stirringThe reaction mixture is stirred at 50° C. for 24 hours
extractionThe product is extracted with 120 mL of methylene chloride
extractionThe aqueous acid layer is extracted again with 25 mL of methylene chloride
concentrationThe combined methylene chloride layers are concentrated by rotary evaporation

Sources & evidence

ORD record: ord-b854180c65674e99b1960f110e2d9bdc
Source dataset: uspto-grants-2005_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06891059B2

Reaction notes

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