Tributylphosphine → HCID 178470442, compound

HRID 989672Notes

Reaction equation

HRID 989672 reaction equation
P(CCCC)(CCCC)CCCC.[N+:14](=[C:16]([C:22]([C:24]1[CH:29]=[C:28]([CH2:30][N:31]2[CH2:36][CH2:35][O:34][CH2:33][CH2:32]2)[CH:27]=[CH:26][C:25]=1F)=[O:23])[C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N-:15]>O1CCOCC1>[OH:23][C:22]1[C:24]2[C:25](=[CH:26][CH:27]=[C:28]([CH2:30][N:31]3[CH2:36][CH2:35][O:34][CH2:33][CH2:32]3)[CH:29]=2)[N:15]=[N:14][C:16]=1[C:17]([O:19][CH2:20][CH3:21])=[O:18]

Participants

4

Reactant 2

HCID 13831TributylphosphineHCID 72594823HCID 72594823, compound

Product 1

HCID 178470442HCID 178470442, compoundYield 6.7%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

A solution of Bu3P (3.90 iL) in dioxane (20 mL) is added to a stirred solution of ethyl 2-diazo-3-[2-fluoro-5-(4-morpholinylmethyl)phenyl]-3-oxopropanoate (Preparation 7, 3.16 g) in dry dioxane (56 mL). The mixture is stirred at room temperature for 30 min then gently refluxed for 1.5 h. The reaction is cooled and concentrated. The crude product is purified by column chromatography (CH2Cl2/MeOH, 99/1; CH2Cl2/MeOH, 98/2; CH2Cl2/MeOH, 95/5) to yield 0.200 g (4.5%) of the desired product as an off-white solid. Additional material can be obtained by heating the acyclic intermediate which was isolated in the chromatography at 130° C. in diglyme (32 mL) for 3.5 h. The resulting mixture is concentrated. The crude product is purified by column chromatography (CH2Cl2/MeOH, 99/1; CH2Cl2/MeOH, 98/2; CH2Cl2/MeOH, 95/5) to yield 0.531 g (30% %) of the desired product as a white solid to give an overall yield of 0.731 g (35%). Physical characteristics are as follows: m.p. 195-197° C. (dec); 1H NMR (DMSO-d6) δ 14.0, 8.01, 7.83, 7.67, 4.30, 3.60, 2.38, 1.30; MS (ESI-) for C16H19N3O4 m/z 316.1 (M—H)−.

Workup

  1. temperaturethen gently refluxed for 1.5 h
  2. temperatureThe reaction is cooled
  3. concentrationconcentrated
  4. customThe crude product is purified by column chromatography (CH2Cl2/MeOH, 99/1; CH2Cl2/MeOH, 98/2; CH2Cl2/MeOH, 95/5)

Sources & evidence

ORD record
ord-5122e5e5838e4c70bfc26932fa12ecd5
Source dataset
uspto-grants-2002_10
Patent number
US06458788B1

Reaction notes

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