Hydrochloric Acid → HCID 69956801, compound

HRID 1168652Notes

Reaction equation

HRID 1168652 reaction equation
[S:1]1[C:5]2[C:6]3[CH:11]=[CH:10][S:9][C:7]=3[S:8][C:4]=2[CH:3]=[C:2]1[C:12]([OH:14])=O.[Al+3].[Cl-].[Cl-].[Cl-].[C:19](Cl)(=O)[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]C.Cl>ClCCl>[C:12]([C:2]1[S:1][C:5]2[C:6]3[CH:11]=[CH:10][S:9][C:7]=3[S:8][C:4]=2[CH:3]=1)(=[O:14])[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8124Octanoyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 69956754HCID 69956754, compound

Product 1

HCID 69956801HCID 69956801, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Dithienothiophene 2 (R1═R2═R3═R4═H) (765 mg, 3.90 mmol) was dissolved in dry dichloromethane (35 cm3) and the solution was ice-cooled before AlCl3 (790 mg, 5.92 mmol) was added in one portion yielding a dark mixture. A solution of octanoyl chloride (1.00 g, 6.02 mmol) in dichloromethane (20 cm3) was added dropwise over a 20 minute period and the mixture was then allowed to stand at room temperature for a further thirty minutes. It was then added to ice and the mixture was acidified with dilute hydrochloric acid (100 cm3). Additional dichloromethane (100 cm3) was added and the layers separated. The organic layer was washed with water, dried over MgSO4 and concentrated. Column Chromatography (hexane—30% dichloromethane/hexane) afforded 790 mg (63%) of the title compound. An analytical sample may be prepared by recrystallisation from a mixture of dichloromethane and methanol. Rf 0.31 (1:1 dichloromethane/hexane); m.p. 130-131° C.; 1H (250 MHz, CDCl3) δ 0.89 (3H, t, J6.5, CH2CH3); 1.25 (8H, br s, CH2CH2CH2); 1.78 (2H, m, CH2CH2CO); 2.93 (2H, t, J7.5, CH2CO); 7.32 (1H, d, J5.0, Dt-H); 7.52 (1H, d, J5.0, Dt-H); 7.91 (1H, s, Dt-H); 13C (100 MHz, CDCl3) δ 14.1; 22.6; 25.0; 29.1; 29.3; 30.9; 31.7; 39.0; 120.9; 125.5; 129.0; 141.4; 144.4; 144.9; 193.7; v (cm−1, KBr) 600, 702, 1191, 1364, 1466, 1493, 1644 (C═O), 2925; Calc. for C16H18S3O C, 59.6; H, 5.6. Found: C, 59.2; H, 5.6.

Workup

  1. additionwas added in one portion
  2. customyielding a dark mixture
  3. waitto stand at room temperature for a further thirty minutes
  4. additionIt was then added to ice
  5. customthe layers separated
  6. washThe organic layer was washed with water
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-734dee132b0c43ffbb555a145ec7a9b7
Source dataset
uspto-grants-2003_09
Patent number
US06626566B2

Reaction notes

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