Stannous Chloride → 6,12-Bis[2-[4-(1,1-dimethylethyl)phenyl]ethynyl]benzo[1,2-b:4,5-b′]bis[1]benzothiophene

HRID 423440Notes

Reaction equation

HRID 423440 reaction equation
[Sn](Cl)Cl.[C:4]([C:8]1[CH:13]=[CH:12][C:11]([C:14]#[C:15][C:16]2(O)[C:27]3[C:26]4[CH:28]=[CH:29][CH:30]=[CH:31][C:25]=4[S:24][C:23]=3[C:22]([C:33]#[C:34][C:35]3[CH:40]=[CH:39][C:38]([C:41]([CH3:44])([CH3:43])[CH3:42])=[CH:37][CH:36]=3)(O)[C:21]3[C:20]4[CH:45]=[CH:46][CH:47]=[CH:48][C:19]=4[S:18][C:17]2=3)=[CH:10][CH:9]=1)([CH3:7])([CH3:6])[CH3:5]>C(O)(=O)C.CC(C)=O>[C:41]([C:38]1[CH:39]=[CH:40][C:35]([C:34]#[C:33][C:22]2[C:21]3[C:20]4[CH:45]=[CH:46][CH:47]=[CH:48][C:19]=4[S:18][C:17]=3[C:16]([C:15]#[C:14][C:11]3[CH:12]=[CH:13][C:8]([C:4]([CH3:6])([CH3:5])[CH3:7])=[CH:9][CH:10]=3)=[C:27]3[C:23]=2[S:24][C:25]2[CH:31]=[CH:30][CH:29]=[CH:28][C:26]=23)=[CH:36][CH:37]=1)([CH3:42])([CH3:43])[CH3:44]

Participants

5

Reactant 2

HCID 24479Stannous ChlorideHCID 57995442HCID 57995442, compound

Product 1

HCID 251177236,12-Bis[2-[4-(1,1-dimethylethyl)phenyl]ethynyl]benzo[1,2-b:4,5-b′]bis[1]benzothiophene

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 180AcetoneSolvent

Conditions

Temperature
8 °C

Procedure

A solution of tin(II)chloride dehydrate (1.82 g, 8.05 mmol) in glacial acetic acid (30 ml) is added within ten minutes to a solution of 6,12-bis-(4-tert-butyl-phenylethynyl)-6,12-dihydro-dibenzo[d,d′]benzo[1,2-b;4,5-b′]dithiophene-6,12-diol (educt 2) in acetone (30 ml). There is a slight temperature increase (8° C.), and formation of a yellow suspension takes place. This suspension is stirred over night at ambient temperature, and then the solid is filtered off. The solid is then washed with water/glacial acetic acid (twice, 30 ml 1:1 v:v), water (twice with 30 ml), and twice with acetone (30 ml). The residue is then dried to give crude product which is recrystallised from anisol (65 ml). The product is filtered off, washed with anisol (8 ml), toluene (2 times 8 ml) and hexane (twice ca. 10 ml) and dried to give the title product as yellow crystals. Mp. (DSC) 349-350° C., MS (m/z 602 (100%), correct isotopic pattern), elementary analysis: C, 84.61%; (calcd. 83.68%); H, 5.89%; (calcd. 5.68%). 1H-NMR (CDCl3, 300 MHz) δ 1.33 (s, 9H, C(CH3)3); 7.41-7.47 (m, 4H, 2 Ph H, 2 benzothiophene H); 7.66 (AA′BB′, 2H, 2 Ph H); 7.84 (m, 1H), 9.15 (m, 1H) (2 benzothiophene H).

Workup

  1. filtrationthe solid is filtered off
  2. washThe solid is then washed with water/glacial acetic acid (twice, 30 ml 1:1 v
  3. customThe residue is then dried
  4. customto give crude product which
  5. customis recrystallised from anisol (65 ml)
  6. filtrationThe product is filtered off
  7. washwashed with anisol (8 ml), toluene (2 times 8 ml) and hexane (twice ca. 10 ml)
  8. customdried

Sources & evidence

ORD record
ord-3ffcaa8e17be4abab83134b3bfdfe7d9
Source dataset
uspto-grants-2012_01
Patent number
US08101776B2

Reaction notes

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