Water → 1,2-Bis(2-methyl-6-formyl-1-benzothiophen-3-yl)cyclopentene

HRID 271630Notes

Reaction equation

HRID 271630 reaction equation
ClC([O:4][CH:5](Cl)Cl)Cl.[Cl-].[Al+3].[Cl-].[Cl-].[CH3:12][C:13]1[S:14][C:15]2[CH:36]=[CH:35][CH:34]=[CH:33][C:16]=2[C:17]=1[C:18]1[CH2:22][CH2:21][CH2:20][C:19]=1[C:23]1[C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][C:26]=2[S:25][C:24]=1[CH3:32].[OH2:37].[N+]([C:41]1C=CC=CC=1)([O-])=O>>[CH3:32][C:24]1[S:25][C:26]2[CH:31]=[C:30]([CH:5]=[O:4])[CH:29]=[CH:28][C:27]=2[C:23]=1[C:19]1[CH2:20][CH2:21][CH2:22][C:18]=1[C:17]1[C:16]2[CH:33]=[CH:34][C:35]([CH:41]=[O:37])=[CH:36][C:15]=2[S:14][C:13]=1[CH3:12]

Participants

6

Reactant 5

HCID 962WaterHCID 7416NitrobenzeneHCID 558102Bis(dichloromethyl) etherHCID 6451240Aluminum(III) ChlorideHCID 153514521,2-Bis(2-methyl-1-benzothiophen-3-yl)cyclopentene

Product 1

HCID 587383351,2-Bis(2-methyl-6-formyl-1-benzothiophen-3-yl)cyclopentene

Conditions

Temperature
0 °C

Procedure

Dichloromethyl ether (4.52 ml, 50 mmol) and anhydrous aluminum chloride (1.78 g, 13.35 mmol) were added to a stirred solution of 1,2-bis(2-methyl-1-benzothiophen-3-yl)cyclopentene 4 (1.2 g, 3.33 mmol) in nitrobenzene (25 ml) at 0° C., and the mixture was stirred for 30 min at 0° C. and for 20 hours at room temperature. The reaction mixture was poured into icy water, and the product was extracted by ethyl acetate, was washed with water and was dried by magnesium sulfate. After distillation of nitrobenzene under vacuum, the product was purified by the column chromatography (Silica Gel, 0.063-0.1) with a petroleum ether (40/70):ethyl acetate mixture (6:1 by volume) being used as an eluent. The yield was 0.56 g of dialdehyde 5 (40%), Tmelt=196-197° C. (hexane:chloroform, 6:1 by volume). Mass spectrum, m/z: 416, [M]+. A 1H NMR spectrum (DMSO-d6, δ, ppm, J/Hz): 2.25 (m, 6H, 2×CH3), 2.97 (br m, 6H, 3×CH2), 7.6-8.5 (br m, 6H, CHarom.), 9.98 (br m, 2H, 2×CHO). The results found (%): C, 72.16; H, 4.86; S, 15.34. C25H20O2S2. The results calculated (%): C, 72.08; H, 4.84; S, 15.40.

Workup

  1. extractionthe product was extracted by ethyl acetate
  2. washwas washed with water
  3. dry with materialwas dried by magnesium sulfate
  4. distillationAfter distillation of nitrobenzene under vacuum
  5. customthe product was purified by the column chromatography (Silica Gel, 0.063-0.1) with a petroleum ether (40/70)
  6. customThe yield was 0.56 g of dialdehyde 5 (40%), Tmelt=196-197° C. (hexane:chloroform, 6:1 by volume)

Sources & evidence

ORD record
ord-12f474d27795466daff41c8b2715e52c
Source dataset
uspto-grants-2008_11
Patent number
US07452950B2

Reaction notes

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