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This post is compatible for submission to ChemSpider Reactions.
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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
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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 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 |
| For step in multistep reaction - link to previous reaction step | |
| For step in multistep reaction - link to following reaction step |
Attached Files
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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 |
| For step in multistep reaction - link to following reaction step |
Attached Files
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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 NaHCO3 (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. Org. Lett. 2004, 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
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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. Comm. 1991, 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