Potassium Fluoride → 1-(3,4-Dimethoxyphenyl)-2-nitro-6-cyano-6-(prop-2-yl)-6-(3,4-dimethoxyphenyl)hexan-3-ol

HRID 979376Notes

Reaction equation

HRID 979376 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH2:11][CH2:12][N+:13]([O-:15])=[O:14])[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].[CH3:16][O:17][C:18]1[CH:19]=[C:20]([C:26]([CH2:32][CH2:33][CH:34]=[O:35])([CH:29]([CH3:31])[CH3:30])[C:27]#[N:28])[CH:21]=[CH:22][C:23]=1[O:24][CH3:25].[F-].[K+]>CC(O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH2:11][CH:12]([N+:13]([O-:15])=[O:14])[CH:34]([OH:35])[CH2:33][CH2:32][C:26]([C:27]#[N:28])([CH:29]([CH3:30])[CH3:31])[C:20]2[CH:21]=[CH:22][C:23]([O:24][CH3:25])=[C:18]([O:17][CH3:16])[CH:19]=2)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10]

Participants

5

Reactant 3

HCID 522689Potassium FluorideHCID 30153703-(3,4-Dimethoxyphenyl)-2-methyl-6-oxohexane-3-carbonitrileHCID 10036050Benzene, 1,2-dimethoxy-4-(2-nitroethyl)-

Product 1

HCID 137457541-(3,4-Dimethoxyphenyl)-2-nitro-6-cyano-6-(prop-2-yl)-6-(3,4-dimethoxyphenyl)hexan-3-olYield 73.9%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A mixture of 2-(3,4-dimethoxyphenyl)-1-nitroethane (4, 135 g, 0.64 mol), 2-(3,4-dimethoxyphenyl)-2-(3-oxopropyl)-2-isopropylacetonitrile (7, 156 g, 0.57 mol) and KF (19.3 g, anhydrous, Aldrich) in 2-propanol (2.0 L) was heated to 50°-55° C. for about 40 hours. The mixture was then cooled to room temperature and the isopropanol removed in vacuo. The residue was dissolved in CH2Cl2 (1.6 L) and filtered through Celite (50 g). The filtrate was extracted with saturated aqueous NaHCO3 (2×500 mL), the organic layer evaporated, and the product recrystallized from ethyl acetate-hexane (1:1) to yield 1-(3,4-dimethoxyphenyl)-2-nitro-6-cyano-6-(i-propyl)-6-(3,4-dimethoxyphenyl)hexan-3-ol (8, 205 g, m.p. 171°-173° C., MS m/e 486 (M+)).

Workup

  1. temperaturewas heated to 50°-55° C. for about 40 hours
  2. customthe isopropanol removed in vacuo
  3. dissolutionThe residue was dissolved in CH2Cl2 (1.6 L)
  4. filtrationfiltered through Celite (50 g)
  5. extractionThe filtrate was extracted with saturated aqueous NaHCO3 (2×500 mL)
  6. customthe organic layer evaporated
  7. customthe product recrystallized from ethyl acetate-hexane (1:1)

Sources & evidence

ORD record
ord-a4b5f385c0054b7390e1b66ef8677de2
Source dataset
uspto-grants-1987_05
Patent number
US04667038

Reaction notes

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