Nitrogen → HCID 54687217, compound

HRID 2394036Notes

Reaction equation

HRID 2394036 reaction equation
C([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7]C=1)(=O)CC.N#N.C(N([CH2:18][CH3:19])CC)C.C[Si](O[S:25]([C:28](F)(F)F)(=O)=O)(C)C.C(O[C:35](=O)[CH:36]([C:42]1S[CH:44]=[CH:45][CH:46]=1)[C:37]([O:39][CH2:40][CH3:41])=O)C.[C:48]([O-])([O-])=[O:49].[Na+].[Na+].C([O:56]CC)C>C(Cl)Cl>[OH:49][C:48]1[C:18]([CH3:19])=[C:37]([C:36]2[CH:35]=[CH:44][CH:45]=[CH:46][CH:42]=2)[O:39][C:40](=[O:56])[C:41]=1[S:25][C:28]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:5]=1

Participants

9

Reactant 7

HCID 947NitrogenHCID 3283Diethyl EtherHCID 71481-Phenyl-1-propanoneHCID 8471TriethylamineHCID 10340Sodium CarbonateHCID 65367Trimethylsilyl triflateHCID 15591544Diethyl (thiophen-2-yl)propanedioate

Product 1

HCID 54687217HCID 54687217, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of propiophenone (1.50 mL, 11.3 mmol) in CH2Cl2 (40.0 mL) was cooled to 0° C. (N2 atmosphere) and treated with triethylamine (3.14 mL, 22.6 mmol) followed by trimethylsilyltriflate (2.60 mL, 13.5 mmol). The solution was then warmed to ambient temperature, allowed to stir for 15 min., and subsequently quenched into a mixture of diethyl ether (50 mL) and saturated aqueous NaHCO3 (20 mL). The layers were separated and the organic layer washed with a 1:1 mixture of brine:saturated NaHCO3 (20 mL). The ethereal solution was then dried with Na2SO4 and the solvent removed in vacuo. The resulting silyl enol ether was then transferred to a flask containing diethyl-2-(thiophenyl)propane-1,3-dioate (1.00 g, 3.76 mmol), the mixture heated to 140° C. for 16 h. then allowed to cool to room temperature where it was diluted with diethylether and extraced with saturated Na2CO3 (3×20 mL). The aqueous layers were combined, washed with diethylether (3×75 mL), then carefully acidified with conc. HCl. The mixture was then extracted with CH2 Cl2 (3×200 mL), the organic layers combined, dried with Na2SO4, and the solvent removed in vacuo to provide the title compound (0.350 g, m.p. 166°-167° C.). 1H NMR (400 MHz, DMSO-d6) δ 6.309-6.285 (m, 2 H), 6.227-6.211 (m, 3 H), 5.983 (t, 2 H, J=8 Hz), 5.862 (d, 3 H, J=8 Hz), 0.705 (s, 3 H).

Workup

  1. customsubsequently quenched into a mixture of diethyl ether (50 mL) and saturated aqueous NaHCO3 (20 mL)
  2. customThe layers were separated
  3. washthe organic layer washed with a 1:1 mixture of brine
  4. dry with materialThe ethereal solution was then dried with Na2SO4
  5. customthe solvent removed in vacuo
  6. customThe resulting silyl enol ether was then transferred to a flask
  7. temperaturethe mixture heated to 140° C. for 16 h.
  8. temperatureto cool to room temperature where it
  9. washwashed with diethylether (3×75 mL)
  10. extractionThe mixture was then extracted with CH2 Cl2 (3×200 mL)
  11. dry with materialdried with Na2SO4
  12. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-291f99b8be9d4039b98fbd07f8ab21d6
Source dataset
uspto-grants-1998_09
Patent number
US05808062

Reaction notes

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