Triethylamine → HCID 18398542, compound

HRID 1018894Notes

Reaction equation

HRID 1018894 reaction equation
[OH:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[C:14]([O:20][CH3:21])[CH:13]=2)[C:10]#[N:11])[CH:5]=[CH:4]1.C(N(CC)CC)C.[C:29]1([P:35](Cl)([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[O:36])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>O1CCCC1>[C:29]1([P:35]([O:1][N:2]=[C:3]2[CH:4]=[CH:5][C:6](=[C:9]([C:12]3[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[C:14]([O:20][CH3:21])[CH:13]=3)[C:10]#[N:11])[CH:7]=[CH:8]2)([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[O:36])[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 73910Diphenylphosphinic chlorideHCID 18398548HCID 18398548, compound

Product 1

HCID 18398542HCID 18398542, compoundYield 119.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
2.5 °C

Procedure

10.16 g (0.036 mol) of (4-Hydroxyimino-cyclohexa-2,5-dienylidene)-3,4-dimethoxyphenylacetonitrile (prepared as described in Example 13.1) and 3.64 g (0.036 mol) of triethylamine are dissolved in 180 ml of tetrahydrofuran and cooled to 0-5° C. 8.52 g (0.036 mol) of diphenylphosphoryl chloride, dissolved in 70 ml of tetrahydrofuran, are added dropwise. When the addition is completed, the ice bath is removed and the solution stirred overnight at room temperature. Water and ethyl acetate are subsequently added, the organic layer is washed several times with saturated sodium chloride solution and water and dried over magnesium sulfate. Evaporation of the solvent gives 20.7 g of a viscous red oil, which is further purified by filtration over silica gel (eluent: hexane/ethyl acetate 9:1). Yield: 11.5 g (62%) (4-diphenylphosphoryloxyimino-cyclohexa-2,5-dienylidene)-3,4-dimethoxyphenyl-acetonitrile, reddish viscous oil which solidifies upon standing. 31P-NMR (CDCl3; δ relative to H3PO4 as external reference): 37.102 and 2.9.092 ppm (P(V) of the (E) and (Z)-isomers). 1H-NM R (CDCl3, δ [ppm]): 7.9-7.75 (m, 4H); 7.55-7.35 (m, 6H), 7.4-6.65 (m, 7H); 3.91/3.90 (s, 3H, (E)/(Z) isomers); 3.89/3,88 (s, 3H, (E)/(Z) isomers).

Workup

  1. additionare added dropwise
  2. additionWhen the addition
  3. customthe ice bath is removed
  4. additionWater and ethyl acetate are subsequently added
  5. washthe organic layer is washed several times with saturated sodium chloride solution and water
  6. dry with materialdried over magnesium sulfate
  7. customEvaporation of the solvent

Sources & evidence

ORD record
ord-e9a0a6a06b4647e0a410eff63daa27b8
Source dataset
uspto-grants-2002_11
Patent number
US06485886B1

Reaction notes

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