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

HRID 1053702노트

반응식

HRID 1053702 반응식
[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]

참가 물질

7

반응물 5

HCID 8058HexaneHCID 10987891Ethyl 1,1-diethoxyethyl(methyl)phosphinate2회HCID 18522661Acetone cardice2회HCID 1182770521-Methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene2회HCID 178418339Butyllithium

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-446ddf3890bb473aa2319200993776f3
출처 데이터셋
uspto-grants-2016_07
특허 번호
US09394236B2

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