Pyrrole → (E)-1-[2-(Biphenyl-4-yloxyl)vinyl]-1H pyrrole

HRID 1053508

Reaction equation

HRID 1053508 reaction equation
I/[CH:2]=[CH:3]/[O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:7][CH:6]=1.[NH:17]1[CH:21]=[CH:20][CH:19]=[CH:18]1.C([O-])([O-])=O.[Cs+].[Cs+]>[Cu]I>[C:8]1([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:9]=[CH:10][C:5]([O:4]/[CH:3]=[CH:2]/[N:17]2[CH:21]=[CH:20][CH:19]=[CH:18]2)=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 8027PyrroleHCID 10796Cesium carbonateHCID 89873752(E)-4-((2-Iodovinyl)oxy)-1,1'-biphenyl

Product 1

HCID 89873682(E)-1-[2-(Biphenyl-4-yloxyl)vinyl]-1H pyrroleYield 86.4%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Procedure

The compound 10 was prepared following the procedure described for 5 with 4 (0.2 g, 0.62 mmol, 1 eq), pyrrole (0.062 g, 0.93 mmol, 1.5 eq), Cs2CO3 (0.40 g, 1.2 mmol, 2.5 eq), CuI (0.059 g, 0.31 mmol, 0.5 eq) and L2 (0.060 g, 0.31 mmol, 0.5 eq) at 70° C. for 12 h to give crude product which were purified by silica gel column chromatography using ethyl acetate-hexane (9:95) to afford compound 10 as white crystals (0.14 g, 85%): mp 102-105° C. Olefinic protons coupling on the named compound gave an AB-system with a typical roof effect with peaks centered at 7.04 and 6.99 ppm. 1H NMR (300 MHz, CDCl3): 7.62-7.53 (m, 4H, HAr), 7.48-7.40 (m, 2H, HAr), 7.38-7.31 (m, 1H, HAr), 7.17-7.09 (m, 2H, HAr), 7.04 (distorted d, 1H, J=11.1 Hz, (O)—CH═CH(N)), 6.99 (distorted d, 1H, J=11.1 Hz, (O)—CH═CH(N)), 6.82 (dd, 2H, J1=4.2 Hz, J2=2.2 Hz, CH═CH of pyrrole), 6.28 (dd, 2H, J1=4.2 Hz, J2=2.2 Hz, CH═CH); 13C NMR (75 MHz, CDCl3): 156.8, 140.4, 136.3, 135.0, 128.8, 128.4, 127.1, 126.9, 119.6, 118.3, 116.5, 110.0 ppm; IR (cm−1): 3086, 3034, 2715, 2682, 1659, 1607, 1587, 1517, 1485, 1360, 1326, 1300, 1239, 1229, 1185, 1173, 1119, 1094, 1072, 1056, 1007, 975, 907, 857, 838, 614; HRMS (ESI) Calculated for C18H15NO [M+H]+ 262.1232. Found 262.1233; Elemental analysis calculated for C18H15NO.0.17H2O: C, 81.77; H, 5.85; N, 5.29. found: C, 81.76; H, 5.91; N, 5.03.

Workup

  1. customThe compound 10 was prepared
  2. customto give crude product which
  3. customwere purified by silica gel column chromatography

Sources & evidence

ORD record
ord-b7a2a21cfa5d4804b1104aa5508ab2db
Source dataset
uspto-grants-2016_07
Patent number
US09393306B2

Linked notes

Loading…