Hydrochloric Acid → 3-{2-Ethyl-6-methyl-4-[3-oxo-3-(3,5,5-trimethyl-4,5,6,7-tetrahydro-benzo[c]thiophen-1-yl)-propenyl]-phenyl}-acrylic acid

HRID 1665954Notes

Reaction equation

HRID 1665954 reaction equation
[CH3:1][C:2]1[S:6][C:5]([C:7](=[O:9])[CH3:8])=[C:4]2[CH2:10][CH2:11][C:12]([CH3:15])([CH3:14])[CH2:13][C:3]=12.[CH2:16]([C:18]1[CH:23]=[C:22]([CH:24]=O)[CH:21]=[C:20]([CH3:26])[C:19]=1[CH:27]=[CH:28][C:29]([OH:31])=[O:30])[CH3:17].Cl>[OH-].[Na+]>[CH2:16]([C:18]1[CH:23]=[C:22]([CH:24]=[CH:8][C:7](=[O:9])[C:5]2[S:6][C:2]([CH3:1])=[C:3]3[CH2:13][C:12]([CH3:15])([CH3:14])[CH2:11][CH2:10][C:4]=23)[CH:21]=[C:20]([CH3:26])[C:19]=1[CH:27]=[CH:28][C:29]([OH:31])=[O:30])[CH3:17]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 574374241-(3,5,5-Trimethyl-4,5,6,7-tetrahydro-benzo[c]thiophen-1-yl)-ethanoneHCID 765393093-(2-Ethyl-4-formyl-6-methyl-phenyl)-acrylic acid

Product 1

HCID 671896023-{2-Ethyl-6-methyl-4-[3-oxo-3-(3,5,5-trimethyl-4,5,6,7-tetrahydro-benzo[c]thiophen-1-yl)-propenyl]-phenyl}-acrylic acidYield 61.1%

Reagents, catalysts & solvents 1

HCID 14798Sodium HydroxideSolvent

Procedure

A solution of 1-(3,5,5-trimethyl-4,5,6,7-tetrahydro-benzo[c]thiophen-1-yl)-ethanone (355 mg, 1.55 mmol) and 3-(2-ethyl-4-formyl-6-methyl-phenyl)-acrylic acid (373 mg, 1.70 mmol, Aldehyde 5) in methanolic NaOH (8 mL, 10 g NaOH in 100 mL methanol) is stirred at rt for 3 h before it is carefully acidified to pH 1 by adding 2 N aq. HCl. The mixture is extracted twice with DCM, the organic extracts are washed with water and brine, dried over MgSO4, filtered and evaporated. The crude product is crystallised from acetonitrile (120 mL) to give 3-{2-ethyl-6-methyl-4-[3-oxo-3-(3,5,5-trimethyl-4,5,6,7-tetrahydro-benzo[c]thiophen-1-yl)-propenyl]-phenyl}-acrylic acid (400 mg) as yellow crystals; LC-MS: tR=1.17 min, [M+1]=423.34; 1H NMR (CDCl3): δ 7.97 (d, J=16.4 Hz, 1H), 7.68 (d, J=15.2 Hz, 1H), 7.33 (s, 2H), 7.28 (d, J=15.8 Hz, 1H), 6.13 (d, J=15.8 Hz, 1H), 3.16 (t, J=7.0 Hz, 2H), 2.77 (q, J=7.6 Hz, 2H), 2.41 (s, 3H), 2.39 (s, 3H), 2.32 (s, 2H), 1.57 (t, J=6.4 Hz, 2H), 1.24 (t, J=7.6 Hz, 3H), 1.00 (s, 6H).

Workup

  1. extractionThe mixture is extracted twice with DCM
  2. washthe organic extracts are washed with water and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe crude product is crystallised from acetonitrile (120 mL)

Sources & evidence

ORD record
ord-0b1a84cdb2f14ab7ba63e7a5730d3b36
Source dataset
uspto-grants-2011_10
Patent number
US08039644B2

Reaction notes

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