Triphenylphosphine → HCID 11218082, compound

HRID 1698907Notes

Reaction equation

HRID 1698907 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[C:32]([O:36][CH2:37][CH3:38])(=[O:35])[CH2:33][OH:34].[CH3:39][C:40]([CH3:47])([CH3:46])[C:41](=O)[CH2:42][C:43]#[N:44]>C1COCC1>[CH3:39][C:40]([CH3:47])([CH3:46])/[C:41](/[O:34][CH2:33][C:32]([O:36][CH2:37][CH3:38])=[O:35])=[CH:42]/[C:43]#[N:44]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 12184Ethyl GlycolateHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 11218082HCID 11218082, compoundYield 80.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 0° C. solution of triphenylphosphine (2.72 g, 10.4 mmol, 1.3 equiv) in anh. THF (50 mL) was treated with diethyl azodicarboxylate (1.81 g, 10.4 mmol, 1.3 equiv), ethyl glycolate (1.08 g, 10.4 mmol, 1.3 equiv) and 4,4-dimethyl-3-oxopentanenitrile (1.00 g, 8.0 mmol). The resulting solution was allowed to warm to room temperature, stirred for 15 h and concentrated under reduced pressure. The residue was purified by flash chromatography (11 cm×22 cm SiO2, gradient from 5% EtOAc/hex to 8% EtOAc/hex) to afford (Z)-4,4-dimethyl-3-(ethoxycarbonylmethoxy)pentenenitrile (1.36 g, 80%) as a colorless oil: TLC (5% EtOAc/hexanes) Rf0.26; 1H NMR (CDCl3) δ1.12 (s, 9H), 1.28 (t, J=7.0 Hz, 3H), 4.24 (q, J=7.0 Hz, 2H), 4.55 (s, 1H), 5.00 (s, 2H); 13C NMR (CDCl3) δ13.9, 27.8, 38.2, 61.5, 67.1, 67.3, 117.0, 167.1, 180.7; CI-LRMS m/z (rel abundance) 212 (M+H, 100%). Anal. Calcd for C11H17NO3: C, 62.54; H, 8.11; N, 6.63. Found: C, 62.57; H, 7.90; N, 6.47.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue was purified by flash chromatography (11 cm×22 cm SiO2, gradient from 5% EtOAc/hex to 8% EtOAc/hex)

Sources & evidence

ORD record
ord-6878b550c6364ca49b3c5cec7d21ac1e
Source dataset
uspto-grants-2002_02
Patent number
US06344476B1

Reaction notes

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