Oxygen → HCID 86608407, compound

HRID 1363994Notes

Reaction equation

HRID 1363994 reaction equation
[I-:1].[OH:2][C:3]1[C:8]([O:9][CH3:10])=[C:7]([O:11][CH3:12])[C:6]([OH:13])=[C:5]([CH3:14])[C:4]=1[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][P+:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.O=O>C(Cl)Cl>[I-:1].[CH3:12][O:11][C:7]1[C:6](=[O:13])[C:5]([CH3:14])=[C:4]([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][P+:20]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)([C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:3](=[O:2])[C:8]=1[O:9][CH3:10]

Participants

4

Reactant 2

HCID 977OxygenHCID 86608408HCID 86608408, compound

Product 1

HCID 86608407HCID 86608407, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 13 (2.07 g) in CH2Cl2 (50 mL) was saturated with oxygen gas and a solution of NO2 in CH2Cl2 (0.5 mL, 1.32 M) was added. The reaction was then stirred at room temperature under an oxygen atmosphere for 18 hrs. The solvent was removed in vacuo to afford the crude product [5-(4,5-dimethoxy-2-methyl-3,6-dioxo-1,4-cyclohexadien-1-yl)pentyl]triphenylphosphonium iodide (14) as a red oil. This residue was re-dissolved in CH2Cl2 (10 mL) and triturated in ether (200 mL) to give an initial yellow precipitate which congealed into a red oil in a few minutes. The solvents were decanted and the precipitate dissolved in CH2Cl2 and the solvent removed in vacuo to give the product (14) (1.866 g) as a red oil. An aliquot (0.880 g) of 14 was purified by column chromatography on silica gel (20 g). Elution with CH2Cl2 gave some unidentified purple coloured material. Elution with 5% ethanol/CH2Cl2 gave the pure iodide product 14 (0.606 g) as a red oil. 1H NMR δ 7.84-7.68 (15H, m, Ar—H) 3.98 (6H, s, 2x Ar—OMe), 3.65 (2H, m, CH2—P+), 2.40 (2H, t, J=7.5 Hz, Ar—CH2), 2.00 (3H, s, Ar-Me), 1.71 (4H, m, —CH2—), 1.43 (2H, m, —CH2—) ppm. 31P NMR (121.4 MHz) δ 25.47 ppm. Anal. calcd. for C32H36IO4P: C, 59.8; H, 5.7; I, 19.8; P, 4.8. Found: C, 60.0; H, 5.3; I, 19.7; P, 4.7%.

Workup

  1. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-fff6daba60c749648b6f46f2a8cbdff0
Source dataset
uspto-grants-2011_02
Patent number
US07888334B2

Reaction notes

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