Tetrahydrofuran → Acequinocyl

HRID 2164721Notes

Reaction equation

HRID 2164721 reaction equation
[C:1]([O:4][C:5]1[C:6](=[O:17])[C:7]2[C:12]([C:13](=[O:16])[C:14]=1[Cl:15])=[CH:11][CH:10]=[CH:9][CH:8]=2)(=[O:3])[CH3:2].[NH4+].[Cl-].[CH2:20]1[CH2:24]O[CH2:22][CH2:21]1>[Cl-].[Cl-].[Zn+2].[Zn]>[CH2:22]([C:5]1[C:6](=[O:17])[C:7]2[C:12]([C:13](=[O:16])[C:14]=1[Cl:15])=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH2:21][CH2:20][CH2:24][CH2:7][CH2:6][CH2:5][CH2:14][CH2:13][CH2:12][CH2:11][CH3:10].[CH2:22]([C:14]1[C:13](=[O:16])[C:12]2[C:7]([C:6](=[O:17])[C:5]=1[O:4][C:1](=[O:3])[CH3:2])=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:21][CH2:20][CH2:24][CH2:7][CH2:6][CH2:5][CH2:14][CH2:13][CH2:12][CH2:11][CH3:10]

Participants

7

Reactant 3

HCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 2751033-Chloro-1,4-dioxo-1,4-dihydronaphthalen-2-yl acetate

Product 2

HCID 93315AcequinocylHCID 1030502-Chloro-3-dodecyl-1,4-naphthoquinone

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 3007855ZincchlorideCatalyst

Procedure

First, 0.60 g (4.4 mmoles) of ZnCl2 was dissolved in 20 mL of THF, and 6.30 g (4.39 mmoles, 0.697 mmoles/g) of dodecyl MgBr was added dropwise. After stirring for 15 minutes, this Zn reagent was added dropwise to 1.00 g (4.0 mmoles) of 2-acetoxy-3-chloro-1,4-naphthoquinone in 50 mL of THF. The mixture was stirred overnight and then poured into 100 mL of NH4Cl solution, extracted with 3×100 mL of ether, dried over MgSO4, filtered, and solvent was removed. The residue was flash-chromatographed to give 2-dodecyl-3-chloro-1,4-naphthoquinone and 2-dodecyl-3-acetoxy-1,4-naphthoquinone. The dodecylchloro derivative was recrystallized from hot ethanol; 0.217 g (0.603 mmoles, 15%). The dodecylacetoxy derivative was further purified by preparative TLC; 0.079 g (0.21 mmoles, 5%) mp: 49° to 51° C. (lit: 57° to 58° C.). 1H NMR (CDCl3, δ): 8.3 (m, 2H), 7.75 (m, 2H), 2.58 (m, 2H), 2.40 (s, 3H), 1.30 (br s, 20H), 0.9 (m, 3H). IR (CHCl3, cm-1): 2935s, 2860m, 1775s, 1679s, 1670sh, 1640m, 1600 m.

Workup

  1. stirringThe mixture was stirred overnight
  2. extractionextracted with 3×100 mL of ether
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customsolvent was removed
  6. customThe residue was flash-chromatographed

Sources & evidence

ORD record
ord-3ed88c533b7e40989ad25a267593bb75
Source dataset
uspto-grants-1985_03
Patent number
US04507241

Reaction notes

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