Phenol → Diethyl 2-{3-[3-(1-Octynyl)phenoxy]propyl}propan-1,3-dioate

HRID 256002Notes

Reaction equation

HRID 256002 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:8]#[C:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[CH:5]=[CH:6][CH:7]=1.O[CH2:17][CH2:18][CH2:19][CH:20]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:21]([O:23][CH2:24][CH3:25])=[O:22].N(C(OCC)=O)=NC(OCC)=O.C1(O)C=CC=CC=1>O1CCCC1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:8]([C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][CH:5]=1)[O:1][CH2:17][CH2:18][CH2:19][CH:20]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:21]([O:23][CH2:24][CH3:25])=[O:22])#[C:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

7

Reactant 4

HCID 996PhenolHCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 294844Diethyl 2-(3-hydroxypropyl)propanedioateHCID 135002601-(3-Hydroxyphenyl)-oct-1-yne

Product 1

HCID 20165396Diethyl 2-{3-[3-(1-Octynyl)phenoxy]propyl}propan-1,3-dioateYield 19%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 11776TriphenylphosphineSolvent2×

Conditions

Temperature
10 °C

Procedure

1-(3-Hydroxyphenyl)-oct-1-yne, (2.20 g, 0.01M) and diethyl 2-(3-hydroxypropyl)propane-1,3-dioate [2.40 g, 0.01M, (prepared by the method of A.G. Just et al, Tet. Letts., 3645-3647, (1979)] were dissolved in dry tetrahydrofuran, (50 ml) and triphenylphosphine, (4.20 g, 0.016M), added. The solution was stirred at 10° C. and diethyl azodicarboxylate, (2.80 g, 0.016M), added dropwise. The reaction was stirred for 0.5 h after which time TLC showed some unreacted phenol remaining. Further aliquots of the alcohol, (2.40 g, 0.01M), triphenylphosphine, (4.20 g, 0.016M) and dietyl azodicarboxylate (2.80 g, 0.016M) were added and the reaction stirred for 0.5 h. Evaporation of the solvent in vacuo gave a red oil which was purified by chromatography on silica gel eluting with dichloromethane→chloroform, to yield 0.770 g (19%) of the title compound as a colourless oil. νmax (film 1580, 1600, 1610, 1740, 1758, 2225 (weak) cm-1 ; δ(CDCl3) 0.87 (3H, distorted t, terminal CH3), 1.26 (6H, t, J 7 Hz, 2×ester CH3), 1.33 (8H, m, alkylene chain), 1.93 (4H, m, OCH2CH2CH2), 2.34 (2H, t, J 6 Hz, acetylenic CH2), 3.37 (1H, t, J 7 Hz, CH), 3.91 (2H, t, J 6 Hz, OCH2), 4.16 (4H, q, J 7 Hz, 2×ester CH2), 7.00 (4H, m, aromatics).

Workup

  1. stirringThe reaction was stirred for 0.5 h after which time TLC
  2. stirringthe reaction stirred for 0.5 h
  3. customEvaporation of the solvent in vacuo
  4. customgave a red oil which
  5. customwas purified by chromatography on silica gel eluting with dichloromethane→chloroform

Sources & evidence

ORD record
ord-d0b48ed9346147f3bf5ac145178ff0d8
Source dataset
uspto-grants-1987_10
Patent number
US04699995

Reaction notes

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