Diisopropylethylamine → 2-((Methoxy)(4-phenoxyphenyl)methylene)malononitrile

HRID 432155Notes

Reaction equation

HRID 432155 reaction equation
[C:1]([C:3]([C:19]#[N:20])=[C:4]([OH:18])[C:5]1[CH:10]=[CH:9][C:8]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:7][CH:6]=1)#[N:2].[CH:21](N(C(C)C)CC)(C)C.C[Si](C=[N+]=[N-])(C)C>C(#N)C.CO.C1COCC1>[C:1]([C:3]([C:19]#[N:20])=[C:4]([O:18][CH3:21])[C:5]1[CH:10]=[CH:9][C:8]([O:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[CH:7][CH:6]=1)#[N:2]

Participants

7

Reactant 3

HCID 81531DiisopropylethylamineHCID 167693TrimethylsilyldiazomethaneHCID 223471552-(Hydroxy-(4-phenoxyphenyl)methylene)propanedinitrile2×

Product 1

HCID 223472272-((Methoxy)(4-phenoxyphenyl)methylene)malononitrile

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

1,1-Dicyano-2-hydroxy-2-(4-phenoxyphenyl)ethene (Intermediate Z) (56.5 g) in 780 mL acetonitrile and 85 mL methanol was stirred under nitrogen at 0° C. while adding 52.5 mL diisopropylethylamine then 150 mL 2M-trimethylsilyldiazomethane in THF. After stirring for 2 days at 20° C., 2 g silica for chromatography was added: no further evolution of nitrogen was noted. The brown-red solution was evaporated in vacuo, the residue dissolved in ethyl acetate and washed well with water then brine, dried and evaporated. The residue was extracted with diethyl ether (3×250 mL), decanting from insoluble oil. Evaporation of the ether extracts gave 22.5 g of 1,1-Dicyano-2-methoxy-2-(4-phenoxyphenyl)ethene as a pale orange solid almost pure by t.l.c. (3:2 ethyl acetate:cyclohexane). The insoluble oil was purified by flash chromatography giving 15.0 g red-orange oil. Combined yield (63%) 1H NMR (DMSO-d6, 400 MHz) 7.71 (d, 2H), 7.48 (m, 2H), 7.29 (m, 1H), 7.16 (m, 4H), 3.93 (s, 3H).

Workup

  1. addition2 g silica for chromatography was added
  2. customThe brown-red solution was evaporated in vacuo
  3. dissolutionthe residue dissolved in ethyl acetate
  4. washwashed well with water
  5. dry with materialbrine, dried
  6. customevaporated
  7. extractionThe residue was extracted with diethyl ether (3×250 mL)
  8. customdecanting from insoluble oil
  9. customEvaporation of the ether

Sources & evidence

ORD record
ord-bbbcc0aea8fb475ea1b82601dacce4da
Source dataset
uspto-grants-2003_12
Patent number
US06660744B1

Reaction notes

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