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29th August 2013 @ 12:13

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Reaction information

*#Reaction file
reactionscheme_29 .cdx
*Reaction file type CDX
*Procedure A 250 mL Schlenk flask containing 4-bromothioanisole (2.03 g, 10.0 mmol), PdCl2 (89 mg, 0.5 mmol, 5 mol%), PPh3 (262 mg, 1.0 mmol,  10 mol%) and CuI (95 mg, 0.5 mmol, 5 mol%), with stirring, was evacuated under high vacuum and refilled with Ar before adding distilled benzene (80 mL). Triethylamine, TEA (4.18 mL, 3.04 g, 30.0 mmol, 3.00 eq.) was then added, followed by phenylacetylene (1.21 mL, 1.12 g, 11.0 mmol, 1.10 eq.) dropwise. The reaction mixture was heated to 70 °C, stirred  for 23 h and then stopped before the disappearance of starting material (4-bromothioanisole Rf 0.32, (6/1) hexane/DCM). The solvent was evaporated, the residue was dissolved in DCM and filtered through Celite521; the solution was then washed with water and brine and dried over MgSO4, to afford, after evaporation of the solvent, a mixture of crude title compound and unreacted starting material (3.118 g). The pure product (white solid, 947 mg, 4.22 mmol, yield 42%) was obtained by column chromatography on silica gel using as eluent (6/1) hexane/DCM (Rf 0.17).
*Yield (%) 42 %
*Type of Yield Isolated pure product
Reference(s)
PhD Thesis - 16Sep2010_final p15.pdf
PhD Thesis - 16Sep2010_final p121-122.pdf
Further information Compound 29: Methyl(4-(2-phenylethynyl)phenyl)sulfane

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files
29th August 2013 @ 12:00

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Reaction information

*#Reaction file
overallscheme_28.cdx
*Reaction file type CDX
*Procedure See child reaction steps
*Yield (%)  
*Type of Yield  
Reference(s)
PhD Thesis - 16Sep2010_final p14.pdf
PhD Thesis - 16Sep2010_final p121.pdf
Further information Compound 28: 1,4-bis(2-(4-(2-(4-methylthio)phenyl)ethynyl)phenyl)ethynyl-2,5-bis(octyl-oxy)-benzene

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps

Reaction 21: Sonogashira Coupling: trimethyl(2-(4-(methylthio)phenyl)ethynyl)silane

Reaction 22: Sonogashira Coupling: 2-(4-(2-(4-bromophenyl)ethynyl)phenyl)methylthioether

Reaction 23: Sonogashira Coupling: trimethyl(2-(4-(2-(4-(methylthio)phenyl)ethynyl)phenyl)ethynyl)silane

Reaction 24: Deprotection of TMS group: 2-(4-(2-(4-(methylthio)phenyl)ethynyl)phenyl)ethynylene

Reaction 26: Nucleophilic substitition of hydroquinone to octylbromide: 1,4-bis(octyloxy)benzene

Reaction 27: Halogenation of 1,4-bis(octyloxy)benzene with Iodine: 1,4-diiodo-2,5-bis(octyloxy)benzene

For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
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29th August 2013 @ 11:57

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Reaction information

*#Reaction file
reactionscheme_28 .cdx
*Reaction file type CDX
*Procedure A 25 mL Schlenk flask containing 1,4-Diiodo-2,5-bis(octyloxy)benzene (152 mg, 0.26 mmol), 2-(4-(2-(4-(Methylthio)phenyl)ethynyl)phenyl)ethynylene (144 mg, 0.58 mmol, 2.23 eq.), PdCl2 (5 mg, 26 μmol, 10 mol%), PPh3 (14 mg, 0.05 mmol, 20 mol%) and CuI (10 mg, 0.05 mmol, 20 mol%) was evacuated and refilled with Ar before adding distilled benzene (5.0 mL). Triethylamine, TEA (0.20 mL, 158 mg, 1.56 mmol, 6.00 eq.) was then added dropwise; the reaction mixture was heated to 70 °C and stirred, in the darkness, for 13 h. The disappearance of starting materials (Rfs 0.65 and 0.42 respec., (2/1) hexane/DCM) was monitored by TLC. The solvent was evaporated, the residue was dissolved in DCM, washed with water and brine and dried over anhydrous MgSO4. After evaporation of the solvent, the crude title compound (261 mg) was column chromatographed on silica gel, using as eluent (5/4) DCM/hexane (Rf 0.46), yielding a mixture of product and impurities with similar Rfs (113 mg); further purification using as eluent (3/2) hexane/DCM (Rf 0.14) afforded the pure product (yellow solid, 86 mg, 104 μmol, yield 40%).
*Yield (%) 40 %
*Type of Yield Isolated pure product
Reference(s)
PhD Thesis - 16Sep2010_final p14.pdf
PhD Thesis - 16Sep2010_final p121.pdf
Further information Compound 28: 1,4-bis(2-(4-(2-(4-methylthio)phenyl)ethynyl)phenyl)ethynyl-2,5-bis(octyl-oxy)-benzene

For multistep reactions (or their steps):

Overall reaction? False
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step

Reaction 24: Deprotection of TMS group: 2-(4-(2-(4-(methylthio)phenyl)ethynyl)phenyl)ethynylene

Reaction 27: Halogenation of 1,4-bis(octyloxy)benzene with Iodine: 1,4-diiodo-2,5-bis(octyloxy)benzene

For step in multistep reaction - link to following reaction step  
Attached Files
29th August 2013 @ 11:46

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Reaction information

*#Reaction file
reactionscheme_27 .cdx
*Reaction file type CDX
*Procedure Repeating the procedure described by Shirai, in a 250 mL rbf a solution of 1,4-bis(Octyloxy)benzene (2.04 g, 6.10 mmol), Hg(OAc)2 (4.84 g, 15.19 mmol, 2.49 eq.) and I2 (3.85 g, 15.17 mmol, 2.49 eq.) in DCM (60 mL) was stirred at r.t. for 19 h. The reaction mixture was filtered through Celite 521 with DCM and the organic phase was washed with Na2S2O3 (aqueous, 10% w/v), to the complete disappearance of the pink colour, then with NaHCO(saturated), water and brine, and dried over anhydrous MgSO4. Evaporation of the solvent and recrystallization from EtOH afforded the pure product (3.15 g, 5.37 mmol, yield 88%).
*Yield (%) 88 %
*Type of Yield Isolated pure product
Reference(s)

PhD Thesis - 16Sep2010_final p14.pdf
PhD Thesis - 16Sep2010_final p120-121.pdf

Shirai, Y.; Zhao, Y. M.; Cheng, L.; Tour, J. M. OrgLett2004, 6, 13, 2129-2132

Further information Compound 27: 1,4-diiodo-2,5-bis(octyloxy)benzene

For multistep reactions (or their steps):

Overall reaction? False
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step Reaction 26: Nucleophilic substitition of hydroquinone to octylbromide: 1,4-bis(octyloxy)benzene
For step in multistep reaction - link to following reaction step Reaction 28: Bidirectional Sonogashira Coupling: 1,4-bis(2-(4-(2-(4-methylthio)phenyl)ethynyl)phenyl)ethynyl-2,5-bis(octyl-oxy)-benzene
Attached Files
29th August 2013 @ 11:23

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Reaction information

*#Reaction file
reactionscheme_26 .cdx
*Reaction file type CDX
*Procedure Repeating the procedure described by Loupy, in a sealed Schlenk tube hydroquinone (0.55 g, 4.99 mmol), Tetrabutylammonium bromide, TBAB (63 mg, 9% w/w KOH) and KOH powder (0.7 g, 12.47 mmol, 2.50 eq.) were stirred for 10 minutes before adding octylbromide (2.16 mL, 2.42 g, 12.53 mmol, 2.51 eq.) and heating to 80 ºC for 17 h. The reaction mixture was then dissolved in Et2O and washed with water, the organic phase was dried over anhydrous MgSO4and the solvent evaporated to afford the crude title compound (1.87 g). The pure product (1.03 g, 3.08 mmol) was obtained by column chromatography on silica gel, using as eluent (5/1) hexane/DCM (Rf0.15); this was then recrystallized from EtOH as white thin flakes (0.77 mg, 2.30 mmol, yield 46%).
*Yield (%) 46 %
*Type of Yield Isolated pure product
Reference(s)

PhD Thesis - 16Sep2010_final p14.pdf
PhD Thesis - 16Sep2010_final p120.pdf

Loupy, A.; Sansoulet, J.; Diez-Barra, E.; Carrillo, J. R. Synth. Comm1991, 21, 1465-1471.

Further information Compound 26: 1,4-bis(octyloxy)benzene

For multistep reactions (or their steps):

Overall reaction? False
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step Reaction 27: Halogenation of 1,4-bis(octyloxy)benzene with Iodine: 1,4-diiodo-2,5-bis(octyloxy)benzene
For step in multistep reaction - link to following reaction step  
Attached Files