Hydrochloric Acid → 4-(3-Cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-carbomethoxyphenylethynyl)cyclohexane

HRID 343552

Reaction equation

HRID 343552 reaction equation
[CH:1]1([O:6][C:7]2[CH:8]=[C:9]([C:15]3([C:25]#[CH:26])[CH2:20][CH2:19][C:18]4([O:24][CH2:23][CH2:22][O:21]4)[CH2:17][CH2:16]3)[CH:10]=[CH:11][C:12]=2[O:13][CH3:14])[CH2:5][CH2:4][CH2:3][CH2:2]1.I[C:28]1[CH:29]=[C:30]([CH:35]=[CH:36][CH:37]=1)[C:31]([O:33][CH3:34])=[O:32].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl>N1CCCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:1]1([O:6][C:7]2[CH:8]=[C:9]([C:15]3([C:25]#[C:26][C:28]4[CH:37]=[CH:36][CH:35]=[C:30]([C:31]([O:33][CH3:34])=[O:32])[CH:29]=4)[CH2:20][CH2:19][C:18]4([O:21][CH2:22][CH2:23][O:24]4)[CH2:17][CH2:16]3)[CH:10]=[CH:11][C:12]=2[O:13][CH3:14])[CH2:2][CH2:3][CH2:4][CH2:5]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 69258Methyl 3-iodobenzoateHCID 110895964-(3-Cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-ethynylcyclohexane

Product 1

HCID 153920314-(3-Cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-carbomethoxyphenylethynyl)cyclohexane

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-ethynylcyclohexane (0.150 g, 0.421 mmol) and methyl 3-iodobenzoate (0.110 g, 0.421 mmol) in piperidine (2.1 mL, dry) under an argon atmosphere was treated with a mixture of tetrakis(triphenylphosphine)palladium(0) (0.020 g, 0.017 mmol), cuprous iodide (0.010 g, 0.053 mmol) and triphenylphosphine (crystal) and the mixture was heated at 80° C. for 40 min. The reaction mixture was chilled to 0° C., was poured into ice-water, was acidified with 3N hydrochloric acid and was extracted five times with methylene chloride. The organic phase was washed with dilute hydrochloric acid, water, saturated brine, was dried over magnesium sulfate, was filtered and concentrated in vacuo. The residue was preadsorbed and chromatographed on silica gel, eluting the with 15 to 20% ethyl acetate in hexanes, to afford a light yellow oil. 1H-NMR (250 MHz, CDCl3) δ 8.11 (t, J=1.4 Hz, 1H), 7.97 (d-d, J=1.3 Hz;J=7.9 Hz, 1H), 7.63 (d-d, J=7.8 Hz;J=1.3 Hz, 1H), 7.39 (t, J=7.8 Hz, 1H), 7.23 (d, J=2.2, 1H), 7.15 (d-d, J=8.4 Hz;J=2.3 Hz, 1H), 6.89 (d, J=8.4 Hz, 1H), 4.80 (m, 1H), 4.00 (s, br, 4H), 3.92 (s, 3H), 3.84 (s, 3H), 2.4 to 1.75 (m, 18H).

Workup

  1. temperatureThe reaction mixture was chilled to 0° C.
  2. extractionwas extracted five times with methylene chloride
  3. washThe organic phase was washed with dilute hydrochloric acid, water, saturated brine
  4. dry with materialwas dried over magnesium sulfate
  5. filtrationwas filtered
  6. concentrationconcentrated in vacuo
  7. customchromatographed on silica gel
  8. washeluting the with 15 to 20% ethyl acetate in hexanes
  9. customto afford a light yellow oil

Sources & evidence

ORD record
ord-9d1ab3a552ae4fc098b65895e585052e
Source dataset
uspto-grants-1999_01
Patent number
US05861421

Linked notes

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