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Diethyl (cyanomethyl)phosphonate → 3-(3-Benzyloxyphenyl)-3-(3,5-dimethoxyphenyl)acrylonitrile

HRID 970989
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HRID 970989 반응식
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([C:15]([C:17]2[CH:22]=[C:21]([O:23][CH3:24])[CH:20]=[C:19]([O:25][CH3:26])[CH:18]=2)=O)[CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(OP([CH2:35][C:36]#[N:37])(=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>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([C:15]([C:17]2[CH:22]=[C:21]([O:23][CH3:24])[CH:20]=[C:19]([O:25][CH3:26])[CH:18]=2)=[CH:35][C:36]#[N:37])[CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

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반응물 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 69203059(3-Benzyloxyphenyl)-(3,5-dimethoxyphenyl)methanoneHCID 692032153-(2,3-Dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrile

생성물 1

HCID 692025963-(3-Benzyloxyphenyl)-3-(3,5-dimethoxyphenyl)acrylonitrile수율 86.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

(3-Benzyloxyphenyl)-(3,5-dimethoxyphenyl)methanone (10.66 g, 30.60 mmol), cyanomethylphosphonic acid diethyl ester (9.63 ml, 61.19 mmol) in anhydrous THF (10 ml), and lithium bis (trimethylsilyl)amide (1.0 M solution in THF, 61.20 ml, 61.19 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 material was purified via flash column chromatography (5% EtOAc in hexane gradient to 30% EtOAc in hexane in about 40 min.) to give 3-(3-benzyloxy-phenyl)-3-(3,5-dimethoxy-phenyl)-acrylonitrile as a white solid (9.82 g, 86%): 1HNMR (DMSO-d6) 7.47-7.31 (m, 6H, Ar), 7.20-6.88 (m, 3H, Ar), 6.66-6.62 (2ts, 1H, Ar), 6.46 (d, J=2 Hz, 2H, Ar), 6.40 (s, 0.5H, double bond proton of one isomer), 6.38 (s, 0.5H, double bond proton of the other isomer), 5.12 (s, 1H, half CH2), 5.11 (s, 1H, half CH2), 3.76 (s, 3H, OCH3), 3.73 (s, 3H, OCH3); 13C NMR(DMSO-d6) δ 161.2, 160.4, 158.4, 158.2, 139.6, 138.9, 138.8, 138.3, 136.7, 129.8, 128.4, 127.9, 127.8, 121.5, 120.8, 117.9, 117.9, 116.8, 116.0, 115.5, 114.4, 107.1, 106.5, 101.9, 101.1, 96.8, 96.5, 69.4, 55.4,53.6; Anal. Calcd. For C24H21NO3: C, 77.61; H, 5.70; N, 3.77. Found: C, 77.39; H, 5.70; N, 3.69.

후처리

  1. customThe crude material was purified via flash column chromatography (5% EtOAc in hexane gradient to 30% EtOAc in hexane in about 40 min.)

출처 및 근거

ORD 기록
ord-e908fdf4f72641caa2877c41082c9f3c
출처 데이터셋
uspto-grants-2007_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07312241B2

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