Triethylamine → p-Nitrobenzyl 2-diazo-3-trimethylsilyloxy-3-butenoate

HRID 2119202Notes

Reaction equation

HRID 2119202 reaction equation
[N+:1](=[C:3]([C:17]([CH3:19])=[O:18])[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)=[O:5])=[N-:2].C(N(CC)CC)C.FC(S(O[Si:35]([CH3:38])([CH3:37])[CH3:36])(=O)=O)(F)F>C(Cl)Cl>[N+:1](=[C:3]([C:17]([O:18][Si:35]([CH3:38])([CH3:37])[CH3:36])=[CH2:19])[C:4]([O:6][CH2:7][C:8]1[CH:9]=[CH:10][C:11]([N+:14]([O-:16])=[O:15])=[CH:12][CH:13]=1)=[O:5])=[N-:2]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 65367Trimethylsilyl triflateHCID 53872938HCID 53872938, compound

Product 1

HCID 54029376p-Nitrobenzyl 2-diazo-3-trimethylsilyloxy-3-butenoateYield 90%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of p-nitrobenzyl α-diazoacetoacetate (236 mg, 1 mmole) and triethylamine (0.15 ml, 1.08 mmole) in CH2Cl2 (2 ml) was added at 0°-5° C. trimethylsilyl trifluoromethylsulfonate (0.22 ml) under a nitrogen atmosphere and the mixture was stirred for 30 minutes. To this clear yellow solution was added dry hexanes (30 ml) and the reaction mixture was stirred for 10 minutes. After removing the oily deposit, the hexanes solution was evaporated in vacuo to yield yellow solid which was redissolved in dry hexanes (50 ml). The insoluble material was filtered over Celite and the filtrate was evaporated in vacuo to obtain 277 mg (0.90 mmole, yield 90%) of the title compound as yellow crystals: ir (film) νmax : 2100 (N2), 1705 (ester), 1520 and 1345 cm-1 (NO2); 1Hmr (CDCl3) δ: 0.27 (9H, s, --SiMe ), 4.23 (1H, d, J=2 Hz, vinyl proton), 4.93 (1H, d, J=2 Hz, vinyl proton), 5.32 (2H, s, --CO2CH2Ar), 7.48 (2H, "d", J=9 Hz, aromatic protons) and 8.23 ppm (2H, "d", J=9 Hz, aromatic protons).

Workup

  1. stirringthe reaction mixture was stirred for 10 minutes
  2. customAfter removing the oily deposit
  3. customthe hexanes solution was evaporated in vacuo
  4. customto yield yellow solid which
  5. filtrationThe insoluble material was filtered over Celite
  6. customthe filtrate was evaporated in vacuo

Sources & evidence

ORD record
ord-6dc52662a6b44883a8a0ffe5c3c4cab3
Source dataset
uspto-grants-1987_07
Patent number
US04683296

Reaction notes

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