Diethyl (cyanomethyl)phosphonate → 3-[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-3-(3,5-dimethoxyphenyl)acrylonitrile

HRID 2378166노트

반응식

HRID 2378166 반응식
[Si:1]([O:8][C:9]1[CH:10]=[C:11]([C:17]([C:19]2[CH:24]=[C:23]([O:25][CH3:26])[CH:22]=[C:21]([O:27][CH3:28])[CH:20]=2)=O)[CH:12]=[CH:13][C:14]=1[O:15][CH3:16])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C(OP([CH2:37][C:38]#[N:39])(=O)OCC)C.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].O1C2C=CC(C(C3C=C(OC)C=C(OC)C=3)=CC#N)=CC=2OCC1>C1COCC1>[C:4]([Si:1]([CH3:2])([CH3:3])[O:8][C:9]1[CH:10]=[C:11]([C:17]([C:19]2[CH:20]=[C:21]([O:27][CH3:28])[CH:22]=[C:23]([O:25][CH3:26])[CH:24]=2)=[CH:37][C:38]#[N:39])[CH:12]=[CH:13][C:14]=1[O:15][CH3:16])([CH3:6])([CH3:5])[CH3:7]

참가 물질

6

반응물 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 692032153-(2,3-Dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrileHCID 69204700[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-(3,5-dimethoxyphenyl)methanone

생성물 1

HCID 692025173-[3-(Tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-3-(3,5-dimethoxyphenyl)acrylonitrile수율 74.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

[3-(tert-butyldimethylsilanyloxy)-4-methoxyphenyl]-(3,5-dimethoxyphenyl) methanone (0.74 g, 1.84 mmol), cyanomethylphosphonic acid diethyl ester (0.58 ml, 3.68 mmol) in anhydrous THF (10 ml), and lithium bis(trimethylsilyl)amide (1.0 M solution in THF, 3.70 ml, 3.68 mmol) were treated in the same manner as described above for the synthesis of 3-(2,3-dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)-acrylonitrile. The crude was purified via flash column chromatography (100% hexane gradient to 20% EtOAc in hexane in about 40 min.) to give 3-[3-(tert-butyl-dimethyl-silanyloxy)-4-methoxy-phenyl]-3-(3,5-dimethoxy-phenyl)-acrylonitrile as an clear colorless oil (0.58 g, 74%): 1HNMR (CDCl3) δ 7.09-6.78 (m, 3H, Ar), 6.53-6.51 (m, 2H, Ar), 6.41 (d, J=2 Hz, 1H, Ar), 5.60 (s, 1H, CH), 3.86-3.76 (multiple singlets, 9H), 0.97 (s, 9H, 3OCH3), 0.14 (s, 6H, 2OCH3). The product was carried over to the next step.

후처리

  1. customThe crude was purified via flash column chromatography (100% hexane gradient to 20% EtOAc in hexane in about 40 min.)

출처 및 근거

ORD 기록
ord-d2022d5ef8924c61a235b1ad6e95aff6
출처 데이터셋
uspto-grants-2008_12
특허 번호
US07470723B2

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