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

HRID 1053702ノート

反応式

HRID 1053702 の反応式
[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]

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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).

後処理

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

出典と根拠

ORDレコード
ord-446ddf3890bb473aa2319200993776f3
出典データセット
uspto-grants-2016_07
特許番号
US09394236B2

反応ノート

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