Methyltriphenylphosphonium iodide → 2,2,12,12-Tetramethyl-7-methylene-tridecanedioic acid diethyl ester

HRID 455758Notes

Reaction equation

HRID 455758 reaction equation
[C:1]1([Li])C=CC=CC=1.[I-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH2:29]([O:31][C:32](=[O:54])[C:33]([CH3:53])([CH3:52])[CH2:34][CH2:35][CH2:36][CH2:37][C:38](=O)[CH2:39][CH2:40][CH2:41][CH2:42][C:43]([CH3:50])([CH3:49])[C:44]([O:46][CH2:47][CH3:48])=[O:45])[CH3:30]>C1COCC1>[CH2:29]([O:31][C:32](=[O:54])[C:33]([CH3:53])([CH3:52])[CH2:34][CH2:35][CH2:36][CH2:37][C:38](=[CH2:1])[CH2:39][CH2:40][CH2:41][CH2:42][C:43]([CH3:50])([CH3:49])[C:44]([O:46][CH2:47][CH3:48])=[O:45])[CH3:30]

Participants

5

Reactant 3

HCID 638159Methyltriphenylphosphonium iodideHCID 117266597-Oxo-2,2,12,12-tetramethyltridecanedioic acid diethyl esterHCID 178506676HCID 178506676, compound

Product 1

HCID 596601732,2,12,12-Tetramethyl-7-methylene-tridecanedioic acid diethyl esterYield 47%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Under nitrogen atmosphere, a solution of phenyllithium (in diethyl ether:cyclohexane=30:70, 7.06 mL, 1.8 M, 12.7 mmol) was added dropwise over 10 min to a solution of methyltriphenylphosphonium iodide (5.52 g, 13.3 mmol) in anhydrous THF (40 mL) at room temperature. The reaction mixture was stirred at room temperature for 30 min, before 2,2,12,12-tetramethyl-7-oxo-tridecanedioic acid diethyl ester (4.5 g, 12.2 mmol) was added and the reaction mixture was stirred for 5 h at 50° C. The resulting light-orange mixture was quenched by adding methanol (0.3 mL), and most of the solvent was removed on a rotary evaporator. The residue was purified by chromatography on silica (hexanes:ethyl acetate=95:5) to furnish the product (2.1 g, 47%) as an oil. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 4.67 (s, 2H), 4.10 (q, 4H, J=7.3 Hz), 1.97 (t, 4H, J=7.6 Hz), 1.6-1.3 (m, 8H), 1.30-1.15 (m, 10H), 1.15 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 178.0, 149.6, 108.6, 60.1, 42.1, 40.6, 35.8, 28.2, 25.1, 24.7, 14.2. HRMS (LSIMS, nba): Calcd. for C22H41O4 (MH+): 369.3004. found 369.3009.

Workup

  1. additionwas added
  2. customThe resulting light-orange mixture was quenched
  3. additionby adding methanol (0.3 mL)
  4. custommost of the solvent was removed on a rotary evaporator
  5. customThe residue was purified by chromatography on silica (hexanes:ethyl acetate=95:5)

Sources & evidence

ORD record
ord-b122d0f462dc43309069d19e0bda8eb8
Source dataset
uspto-grants-2013_07
Patent number
US08497301B2

Reaction notes

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