Triethylamine → (E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)acryloyl azide

HRID 1852060ノート

反応式

HRID 1852060 の反応式
[O:1]1[CH2:6][CH2:5][O:4][C:3]2[C:7](/[CH:11]=[CH:12]/[C:13]([OH:15])=O)=[CH:8][CH:9]=[CH:10][C:2]1=2.C1(P([N:30]=[N+:31]=[N-:32])(C2C=CC=CC=2)=O)C=CC=CC=1.CCN(CC)CC>C1C=CC=CC=1>[O:1]1[CH2:6][CH2:5][O:4][C:3]2[C:7](/[CH:11]=[CH:12]/[C:13]([N:30]=[N+:31]=[N-:32])=[O:15])=[CH:8][CH:9]=[CH:10][C:2]1=2

参加物

5

反応物 3

HCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 5343159(E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)acrylic acid

生成物 1

HCID 86683170(E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)acryloyl azide収率 84.5%

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

(E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)acrylic acid (5 g, 24.25 mmol), diphenylphosphoryl azide (4.96 mL, 23.04 mmol), and Et3N (6.76 mL, 48.5 mmol) were dissolved in benzene and stirred for 16 h. The solution was concentrated under vacuum and the residue was purified by silica gel chromatography using 20% EtOAc/Hexanes to give 4.5 g of (E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-5-yl)acryloyl azide as a yellow solid, which was taken into PhCH2Ph (50 mL). The resulting solution was slowly heated to 80° C. for 1 h and then to reflux for 3 h. After cooling to rt, the solid was collected washing with benzene to give 3.5 g of the desired product 2,3-dihydro-[1,4]dioxino[2,3-f]isoquinolin-7-ol as a solid. 1H NMR (400 MHz, CD3OD) δ ppm 4.37 (m, 4H), 6.83 (d, J=7.09 Hz, 1H), 7.02 (d, J=8.80 Hz, 1H), 7.12 (d, J=7.34 Hz, 1H), 7.79 (d, J=8.80 Hz, 1H); MS: (M+H)+ 204.

後処理

  1. concentrationThe solution was concentrated under vacuum
  2. customthe residue was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-f4bfd13f1eab46d4a6d799a38b10c652
出典データセット
uspto-grants-2015_02
特許番号
US08957203B2

反応ノート

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