Cesium fluoride → 5-(2-Tetracenyl)-2,2'-bithiophene

HRID 1178317Notes

Reaction equation

HRID 1178317 reaction equation
[F-].[Cs+].Cl[C:4]1[CH:21]=[CH:20][C:19]2[C:6](=[CH:7][C:8]3[C:17]([CH:18]=2)=[CH:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=3)[CH:5]=1.C([Sn](CCCC)(CCCC)[C:27]1[S:31][C:30]([C:32]2[S:33][CH:34]=[CH:35][CH:36]=2)=[CH:29][CH:28]=1)CCC.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[CH:5]1[C:6]2[C:19](=[CH:18][C:17]3[C:8]([CH:7]=2)=[CH:9][C:10]2[C:15](=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:16]=3)[CH:20]=[CH:21][C:4]=1[C:27]1[S:31][C:30]([C:32]2[S:33][CH:34]=[CH:35][CH:36]=2)=[CH:29][CH:28]=1

Participants

7

Reactant 4

HCID 25953Cesium fluorideHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 11201877Stannane, [2,2'-bithiophen]-5-yltributyl-HCID 123364632-Chlorotetracene

Product 1

HCID 222454165-(2-Tetracenyl)-2,2'-bithiophene

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Pd2(dba)3 (21 mg, 0.023 mmol, 1.5%), CsF (511 mg, 3.37 mmol, 2.2 eq), dioxane (25 mL), 2-chlorotetracene (403 mg, 1.53 mmol), 5-tri-n-butylstannyl-2,2′-bithiophene (766 mg, 1.68 mmol), P(t-Bu)3 (0.26 mL, 0.090 mmol, 6%) were mixed, bubbled with N2 via cannula for 30 min, and then heated at 100° C. for 16 h. An additional charge of 10 mg of Pd[P(t-Bu)3]2 and 140 mg 5-tri-n-butylstannyl-2,2′-bithiophene and heated at 100° C. for another 24 h. Cooled the mixture and poured on a glass filter frit (10-15 μm pores) and washed the reddish crude with Et2O, water, and air-dried. Gradient sublimation at a source temperature of 250-270° C. afforded 443 mg (74%, on 2-chlorotetracene) of bright orange-red product. DSC: 341° C. (mp, ΔH=87 Jg−1). EIMS: 392 ([M]+, 100%), 196 ([M]2+, 20%). Anal. Calcd. for C26H16S2: C, 79.6; H, 4.1. Found: C, 80.0; H, 4.34.

Workup

  1. custombubbled with N2 via cannula for 30 min
  2. additionAn additional charge of 10 mg of Pd[P(t-Bu)3]2 and 140 mg 5-tri-n-butylstannyl-2,2′-bithiophene
  3. temperatureheated at 100° C. for another 24 h
  4. temperatureCooled the mixture
  5. additionpoured on a glass
  6. filtrationfilter frit (10-15 μm pores)
  7. washwashed the reddish crude with Et2O, water
  8. customair-dried
  9. customGradient sublimation at a source temperature of 250-270° C. afforded 443 mg (74%, on 2-chlorotetracene) of bright orange-red product
  10. custom341° C. (mp, ΔH=87 Jg−1)

Sources & evidence

ORD record
ord-ef4ea42e969846c2a7998c1705b5ffb1
Source dataset
uspto-grants-2007_10
Patent number
US07276395B2

Reaction notes

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