4-Nitrobenzaldehyde → HCID 5388588, compound

HRID 1794344Notes

Reaction equation

HRID 1794344 reaction equation
O1CCCC1.[N+:6]([C:9]1[CH:16]=[CH:15][C:12]([CH:13]=O)=[CH:11][CH:10]=1)([O-:8])=[O:7].[CH2:17]([O:19][P:20]([CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])([O:22][CH2:23][CH3:24])=[O:21])[CH3:18].CN1CCOCC1>[Ti](Cl)(Cl)(Cl)Cl.O>[CH2:23]([O:22][P:20](/[C:25](/[C:26]([O:28][CH2:29][CH3:30])=[O:27])=[CH:13]/[C:12]1[CH:15]=[CH:16][C:9]([N+:6]([O-:8])=[O:7])=[CH:10][CH:11]=1)([O:19][CH2:17][CH3:18])=[O:21])[CH3:24]

Participants

7

Reactant 4

HCID 5414-NitrobenzaldehydeHCID 79724-MethylmorpholineHCID 8028TetrahydrofuranHCID 13345Triethyl phosphonoacetate

Product 1

HCID 5388588HCID 5388588, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolvent

Procedure

To a mixture of titanium tetrachloride (20.0 g) and tetrahydrofuran (100 ml) were added 4-nitrobenzaldehyde (8.00 g) and ethyl diethylphosphonoacetate (11.9 g) under ice-cooling, and N-methylmorpholine (21.4 g) was added. The mixture was stirred at room temperature for 1 hr. The reaction mixture was poured into water and the mixture was extracted with ethyl acetate. The ethyl acetate layer was concentrated to give crystals of 4-[(E)-2-(diethylphosphono)-2-ethoxycarbonylethenyl]nitrobenzene (15.7 g, yield 83%), which were recrystallized from dichloromethane-isopropyl ether to give a colorless prism (14.0 g). melting point: 60–61° C. A mixture of this compound (5.00 g), iron (3.13 g), conc. hydrochloric acid (7 ml) and ethanol (30 ml) was stirred at room temperature for 30 min. The reaction mixture was poured into water and the mixture was extracted with ethyl acetate. The ethyl acetate layer was concentrated, and the residue was subjected to silica gel column chromatography to give crystals of 4-[(E)-2-(diethylphosphono)-2-ethoxycarbonylethenyl]aniline (2.40 g, yield 52%) from a fraction eluted with ethyl acetate-hexane (2:1, v/v), which were recrystallized from acetone-isopropyl ether to give a pale yellow needle (1.75 g). melting point: 79–80° C.

Workup

  1. temperaturecooling
  2. extractionthe mixture was extracted with ethyl acetate
  3. concentrationThe ethyl acetate layer was concentrated

Sources & evidence

ORD record
ord-8d981b5914b743e8a60eb9282957c89e
Source dataset
uspto-grants-2006_04
Patent number
US07022725B2

Reaction notes

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