Hexane → 2-[1-[(1,1-Diethoxyethyl(ethoxy)phosphoryl)methyl]-2-nitro-ethyl]-1-methyl-4-nitro-benzene

HRID 1053702Notes

Reaction equation

HRID 1053702 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1/[CH:11]=[CH:12]/[N+:13]([O-:15])=[O:14].[CH2:16]([O:18][C:19]([P:24]([O:27][CH2:28][CH3:29])([CH3:26])=[O:25])([O:21][CH2:22][CH3:23])[CH3:20])[CH3:17].C(=O)=O.CC(C)=O.C([Li])CCC.CCCCCC>O1CCCC1>[CH2:22]([O:21][C:19]([P:24]([CH2:26][CH:11]([C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[CH3:1])[CH2:12][N+:13]([O-:15])=[O:14])([O:27][CH2:28][CH3:29])=[O:25])([O:18][CH2:16][CH3:17])[CH3:20])[CH3:23]

Participants

7

Reactant 5

HCID 8058HexaneHCID 10987891Ethyl 1,1-diethoxyethyl(methyl)phosphinate2×HCID 18522661Acetone cardice2×HCID 1182770521-Methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene2×HCID 178418339Butyllithium

Product 1

HCID 1182769402-[1-[(1,1-Diethoxyethyl(ethoxy)phosphoryl)methyl]-2-nitro-ethyl]-1-methyl-4-nitro-benzene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Adapting literature known protocols (U.S. Pat. No. 8,344,028; and Baylis, Tetrahedron Lett., 1995, 36(51), 9385-9388), 2-[1-[(1,1-diethoxyethyl(ethoxy)phosphoryl)-methyl]-2-nitro-ethyl]-1-methyl-4-nitro-benzene (19b) is prepared from 1-methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene (19a) through 1,4-conjugate addition of lithiated commercial 1-[1-ethoxy-1-(ethoxy(methyl)phosphoryl)ethoxy]ethane (Baillie, et al., U.S. Pat. No. 4,339,443 (1982). To a solution of [1-ethoxy-1-(ethoxy(methyl)phosphoryl)ethoxy]ethane (2.65 mL, 2.69 g, 12.0 mmol) in anhydrous tetrahydrofuran (THF) (15 mL) and under a nitrogen atmosphere and at a temperature of about −78° C. (dry ice/acetone bath) is dropwise added a solution of n-butyllithium (nBuLi) in hexane (12.0 mL, 12.0 mmol). After about 30 min, the solution of the lithiated compound is added via a cannula within about 5 minutes to a cooled solution (−78° C.; dry ice/acetone bath, nitrogen atmosphere) of (19a) (2.08 g, 10.0 mmol) in anhydrous tetrahydrofuran (THF) (15 mL). The reaction is stirred at this temperature for about 30 minutes followed by gradual warming to about 0° C. (ice/water bath). Stirring is continued at this temperature for another 30 minutes. Aqueous work-up and purification by silica gel column chromatography using ethyl acetate (EtOAc) and hexanes mixtures afford the title compound (19b).

Workup

  1. stirringStirring
  2. waitis continued at this temperature for another 30 minutes
  3. customAqueous work-up and purification by silica gel column chromatography

Sources & evidence

ORD record
ord-446ddf3890bb473aa2319200993776f3
Source dataset
uspto-grants-2016_07
Patent number
US09394236B2

Reaction notes

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