Bis(2-pyridyl) ketone → (Z)-Hex-2-enoic acid

HRID 378745

反応式

HRID 378745 の反応式
N1C=CC=CC=1[C:7]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11]N=1)=[O:8].[Br-].[C:16]([CH2:19][CH2:20][CH2:21]C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)(O)=[O:17].CC([O-])(C)C.[K+].CO.[CH3:50][C:51]([OH:53])=[O:52].C(Cl)Cl>C1COCC1>[C:7]([OH:17])(=[O:8])/[CH:9]=[CH:14]/[CH2:13][CH2:12][CH3:11].[C:51]([OH:53])(=[O:52])/[CH:50]=[CH:16]\[CH2:19][CH2:20][CH3:21]

参加物

7

反応物 4

HCID 88065Bis(2-pyridyl) ketoneHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 21877243DCM MeOH AcOHHCID 23665647Potassium tert-butoxide

生成物 2

HCID 52827072-Hexenoic acid, (2E)-HCID 12467038(Z)-Hex-2-enoic acid収率 19.8%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

Prepared as above from 150.0 mg (0.35 mmol) of the pyridyl ketone, 308.2 mg (0.70 mmol) of (4-carboxy-butyl)triphenylphosphonium bromide, and 1.4 mL (1.4 mmol) of 1.0 M t-BuOK in 1.5 mL of THF at 0° C. for :1.5 hr. Flash chromatography followed by preparative HPLC with MeOH-AcOH-CH2Cl2 (3.5:1.5:95) furnished 107.9 mg 60.2%) of (E)-hexenoic acid and 35.4 mg (19.8%) of (Z)-hexenoic acid (E/Z=3:1). The title (E)-isomer was characterized as follows: mp 86-90° C.; 1H NMR (CDCl3) δ8.55 (br s, 1H), 8.45 (d, J=4.7 Hz, 1H), 8.25 (s, 1H), 8.04 (d, J=8.1 Hz, 2H), 7.47 (d, J=8.0 Hz, 1H), 7.29 (d, J=8.2 Hz, 2H), 7.21 (m, 1H), 7.12 (distorted t, J=~5.1 Hz, 1H), 6.19 (t, J=7.5 Hz, 1H), 3.44 (dt, J=7.0, 6.7, Hz, 2H), 2.34 (t J=7.1 Hz, 2H), 2.25 (dt, J=7.4, 7.3 Hz, 2H), 1.68-0.82 (m, 19H); FDMS 516 (M+1). Anal. (C31H37N3O4) C, H, N.

出典と根拠

ORDレコード
ord-5f4868b847fb4fb7b21085bf149ea1cb
出典データセット
uspto-grants-2000_02
特許番号
US06031095

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