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Chemical Structure| 769-26-6 Chemical Structure| 769-26-6

Structure of 769-26-6

Chemical Structure| 769-26-6

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Krzysztof Kuciński ; Grzegorz Hreczycho ;

Abstract: Commercially available and inexpensive potassium bis(trimethylsilyl)amide (KHMDS) serves as an efficient transition metal-free catalyst for the catalytic sp C−H silylation of several terminal alkynes including two pharmaceuticals. Overall, the presented system allows the synthesis of various attractive silylacetylenes under mild conditions, making this approach an environmentally benign and sustainable alternative to existing synthetic solutions.

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Product Details of [ 769-26-6 ]

CAS No. :769-26-6
Formula : C11H12
M.W : 144.21
SMILES Code : CC1=C(C#C)C(C)=CC(C)=C1
MDL No. :MFCD07777099
InChI Key :VBEPMNWLWNKUGJ-UHFFFAOYSA-N
Pubchem ID :136610

Safety of [ 769-26-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H227
Precautionary Statements:P210-P264-P270-P280-P301+P312-P330-P370+P378-P403+P235-P501

Application In Synthesis of [ 769-26-6 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 769-26-6 ]

[ 769-26-6 ] Synthesis Path-Downstream   1~35

  • 3
  • [ 769-26-6 ]
  • [ 4493-01-0 ]
YieldReaction ConditionsOperation in experiment
With copper(l) iodide; N,N,N,N,-tetramethylethylenediamine; In acetone; at 20℃; for 24h; General procedure: The acetylene derivative (1.0 equiv.) was added to the solution of TMEDA (1.0 equiv.) and CuI (5 mol%)in acetone (ca. 0.05 M) and the reaction mixture was stirred at room temperature. After stirring at room temperature for 24 h, the mixture was concentrated under reduced pressure and extracted with CHCl3 and water. The organic layer was washed with saturated NH4Cl aq. and dried over MgSO4. After removal of thesolvent under reduced pressure, the residue was purified by column chromatography on SiO2 (CC) to give the corresponding butadiyne 2. Further purification was carried out a recyclable preparative HPLC, if necessary.
  • 6
  • [ 769-26-6 ]
  • [ 1667-01-2 ]
YieldReaction ConditionsOperation in experiment
80% With hydrogenchloride; water; copper(l) chloride; In methanol; at 20℃; for 6h;Irradiation; Inert atmosphere; General procedure: A 10 mL reaction vessel with a magnetic stirring bar was equipped with phenylacetylene (1 mmol), CuCl (1 mol%), HCl (0.2 mL, 37 wt %) and methanol (2 mL). The mixture was irradiated with a blue LED (5 W) and stirred under at r.t. in an air atmosphere for 6 h. The distance of the reaction vial from the light is about 2 centimeter. After the reaction, the solvent was removed under reduced pressure. Purification of the crude product was achieved by flash column chromatography using petrol ether/ethyl acetate (6:1~10:1) as eluent.
  • 8
  • [ 769-26-6 ]
  • [ 54353-18-3 ]
  • Phenyl-[1-(2,4,6-trimethyl-phenyl)-vinyl]-phosphinic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl ester [ No CAS ]
  • 9
  • [ 834905-42-9 ]
  • [ 769-26-6 ]
  • 1,1-di-tert-butyl-2,5-bis[(2,4,6-trimethylphenyl)ethynyl]-3,4-diphenylsilole [ No CAS ]
  • 10
  • 2-bromo-1,1-di-tert-butyl-5-phenylethynyl-3,4-diphenylsilole [ No CAS ]
  • [ 769-26-6 ]
  • 1,1-di-tert-butyl-2-[(2,4,6-trimethylphenyl)ethynyl]-5-phenylethynyl-3,4-diphenylsilole [ No CAS ]
  • 11
  • [ 769-26-6 ]
  • [ 686290-22-2 ]
  • 1,1-dimethyl-2,5-bis[(2,4,6-trimethylphenyl)ethynyl]-3,4-diphenylsilole [ No CAS ]
  • 12
  • [ 769-26-6 ]
  • [ 686290-23-3 ]
  • 2-chloro-1,1-dimethyl-5-[(2,4,6-trimethylphenyl)ethynyl]-3,4-diphenylsilole [ No CAS ]
  • 13
  • [ 624-92-0 ]
  • [ 769-26-6 ]
  • 1-methylthio-1-(2,4,6-trimethylphenyl)ethene [ No CAS ]
  • 1-methylthio-2-(2,4,6-trimethylphenyl)ethyne [ No CAS ]
  • 14
  • [ 769-26-6 ]
  • [ 882-33-7 ]
  • 1-phenylthio-1-(2,4,6-trimethylphenyl)ethene [ No CAS ]
  • 1-phenylthio-2-(2,4,6-trimethylphenyl)ethyne [ No CAS ]
  • 15
  • [ 929887-22-9 ]
  • [ 769-26-6 ]
  • 1,1-dimethyl-3,4-bis(2,4,6-trimethylphenyl)silole [ No CAS ]
  • [ 1006881-80-6 ]
  • 16
  • [ 769-26-6 ]
  • [ 106-94-5 ]
  • [ 1142802-51-4 ]
  • 17
  • [ 769-26-6 ]
  • [ 144981-85-1 ]
  • [ 1142802-80-9 ]
  • 18
  • [ 769-26-6 ]
  • [ 87-42-3 ]
  • [ 1160463-40-0 ]
  • 19
  • [ 769-26-6 ]
  • [ 85331-33-5 ]
  • [ 1186638-10-7 ]
YieldReaction ConditionsOperation in experiment
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 50℃; for 3h; A solution of 3,5-dichloropicolinonitrile (1.0 eq.), <strong>[769-26-6]2-ethynyl-1,3,5-trimethylbenzene</strong> (commercially available) (1.0 eq.), trans-dichlororbis(triphenylphosphine)palladium (II) (10 mol %), copper (I) iodide (20 mol %), and triethylamine (5.0 eq.) in DMF (0.3 M) was stirred at 50 C. for 3 hours. After cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate and 10% aqueous ammonium hydroxide. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated en vaccuo. The crude material was purified by flash chromatography on a COMBIFLASH system (ISCO) using 0-10% ethyl acetate in hexane to give 3-chloro-5-(mesitylethynyl)picolinonitrile a as white solid.
With triethylamine;copper(l) iodide; trans-dichlorobis(triphenylphosphine)platinum(II); In N,N-dimethyl-formamide; at 50℃; for 3h; A solution of 3,5-dichloropicolinonitrile (1.0 eq.), 2-ethynyl-l,3,5-trimethylbenzene(commercially available) (1.0 eq.), trans-dichlororbis(triphenylphosphine)palladium (II) (10 mol%), copper (I) iodide (20 mol%), and triethylamine (5.0 eq.) in DMF (0.3 M) was stirred at 500C for 3 hours. After cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate and10% aqueous ammonium hydroxide. The two phases were separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated en vaccuo. The crude material was purified by flash chromatography on a COMBIFLASH system (ISCO) using 0-10% ethyl acetate in hexane to give3-chloro-5-(mesitylethynyl)picolinonitrile a as white solid.
  • 20
  • [ 273-53-0 ]
  • [ 769-26-6 ]
  • [ 1226889-57-1 ]
  • 22
  • [ 54515-11-6 ]
  • [ 769-26-6 ]
  • [ 939985-16-7 ]
  • 23
  • [ 769-26-6 ]
  • [ 1236300-95-0 ]
  • C37H34O5 [ No CAS ]
  • [ 1256651-26-9 ]
  • 25
  • [ 769-26-6 ]
  • [ 3485-80-1 ]
  • [ 1261279-43-9 ]
  • 26
  • [ 726175-82-2 ]
  • [ 769-26-6 ]
  • 1,3-bis-(2,6-diisopropylphenyl)-4-(2,4,6-trimethylphenyl)-1H-1,2,3-triazolium hexafluorophosphate [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% Example 18; 8a 9b 10ab (57%)[0128] l,3-Bis(2,6-diisopropylphenyl)-4-(2,4,6-trimethylphenyl)-lH-l,2,3-triazolium hexafluorophosphate (lOab). To a stirred suspension of triazene 8a (1098 mg, 3 mmol) and anhydrous potassium hexafluorophosphate (750 mg, 4 mmol) in dry dichloromethane (20 mL) in the dark at -78C is added tert-butyl hypochlorite (500 μ, 4.4 mmol), upon which the mixture instantly darkens. Stirring is pursued at -78C for 30 min, and <strong>[769-26-6]mesitylacetylene</strong> 9b (650 μ, -4.6 mmol) is added. The mixture is stirred overnight as it is slowly allowed to warm to room temperature. The contents are then filtered, and the solid residue is washed with dichloromethane. The filtrate is collected, and volatiles are evaporated under reduced pressure. Diethyl ether is then added, and the mixture is vigorously triturated for ca. Ihour, with occasional scratching of the glass surfaces to ensure efficient mixing. Filtration and washing with copious quantities of diethyl ether afford, after drying under vacuum, triazolium salt lOab as an off-white solid (1.11 g, 57%). Analytical samples were obtained after recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of lOab. 1H-NMR (CD3CN, 300 MHz): δ = 9.11 (s, 1H), 7.79 (t, J = 7.8 Hz, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.58 (d, J = 7.8 Hz, 2H), 7.45 (d, J = 7.8 Hz, 2H), 7.06 (s, 2H), 2.34 (sept, J = 6.8 Hz, 2H), 2.31 (sept, J = 6.8 Hz, 2H), 2.27 (s, 3H), 2.15 (s, 6H), 1.32 (d, J = 6.8 Hz, 6H), 1.22 (d, J = 6.8 Hz, 6H), 1.10 (d, J = 6.8 Hz, 6H), 1.02 (d, J = 6.8 Hz, 6H). 13C-NMR (CD3CN, 75 MHz): δ = 146.5, 146.3, 145.8, 144.0, 139.6, 135.9, 134.63, 134.57, 131.3, 130.8, 130.6, 126.6, 126.2, 30.8, 30.4, 26.6, 24.4, 24.2, 21.7, 21.4, 21.3. M.p.: >250C. HR-MS (ESI): Calcd. for C35H46N3 [M+]: 508.3686, found 508.3687.
  • 27
  • [ 769-26-6 ]
  • [ 794-50-3 ]
  • 1,3,4-tris(2,4,6-trimethylphenyl)-1H-1,2,3-triazolium hexafiuorophosphate [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% Example 36; 8b 9b 10bb (88%)[0146] l,3,4-Tris(2,4,6-trimethylphenyl)-lH-l,2,3-triazolium hexafiuorophosphate (lObb). To a stirred suspension of triazene 8b (5.63 g, 20 mmol) and <strong>[769-26-6]mesitylacetylene</strong> 9b (5.76 g, 40 mmol) in dry dichloromethane (100 mL) in the dark at -78C is added tert-butyl hypochlorite (3.33 mL, 30 mmol), upon which the mixture instantly darkens. The mixture is stirred overnight as it is slowly allowed to warm to room temperature. Volatiles are evaporated under reduced pressure, and the crude solid is redissolved in acetone (50 mL), to which is then added potassium hexafiuorophosphate (3.68 g, 20 mmol). The mixture is stirred at room temperature for ca. Ihour, filtered, and the solid residue is washed with dichloromethane. The collected filtrate is evaporated under reduced pressure. Diethyl ether is then added, and the mixture is vigorously triturated for ca. Ihour, with occasional scratching of the glass surfaces to ensure efficient mixing. Filtration and washing with copious quantities of diethyl ether afford, after drying under vacuum, triazolium salt lObb as an off-white solid (10.10 g, 88%). Analytical samples were obtained after recrystallization by vapor diffusion of diethyl ether in an acetonitrile solution of lObb. 1H-NMR (CD3CN, 300 MHz): δ = 8.94 (s, 1H), 7.27 (s, 2H), 7.10 (s, 2H), 7.05 (s, 2H), 2.43 (s, 3H), 2.31 (s, 3H), 2.28 (s, 3H), 2.25 (s, 6H), 2.17 (s, 6H), 2.06 (s, 6H). 13C-NMR (CD3CN, 75 MHz): δ = 145.2, 144.5, 144.3, 143.9, 139.6, 135.7, 135.2, 132.4, 131.7, 131.5, 131.3, 131.1, 130.9, 119.0, 21.5, 21.4, 21.3, 19.1, 17.9. HR-MS (ESI): Calcd. for C29H34N3 [M+]: 424.2747, found 424.2758.
  • 28
  • 1-(4-methylbenzenesulfonyl)-4-(4-methylphenyl)-1,2,3-triazole [ No CAS ]
  • [ 769-26-6 ]
  • [ 1312297-82-7 ]
  • 29
  • [ 1078739-20-4 ]
  • [ 769-26-6 ]
  • [ 1312297-70-3 ]
  • 30
  • [ 769-26-6 ]
  • [ 1312297-99-6 ]
  • [ 1312297-96-3 ]
  • 31
  • 1,3,5-trimethyl-2-[(2-trimethylsilyl)ethynyl]benzene [ No CAS ]
  • [ 769-26-6 ]
  • 32
  • [ 769-26-6 ]
  • (S)-3,3'-diazido-2,2'-bis(methoxymethoxy)-1,1'-binaphthalene [ No CAS ]
  • (S)-1,1'-(2,2'-bis(methoxymethoxy)-[1,1'-binaphthalene]-3,3'-diyl)bis(4-mesityl-1H-1,2,3-triazole) [ No CAS ]
YieldReaction ConditionsOperation in experiment
35% With copper(II) sulfate; sodium L-ascorbate; In dichloromethane; water; tert-butyl alcohol; at 50℃; General procedure: A stirring solution of azide (1.0 eq.), the corresponding alkyne(3 eq.), 0.04 M aq. CuSO4(8 mol%) and 0.12 M aq. sodium ascorbate(24 mol%) in a mixture of CH2Cl2/t-BuOH/H2O (1:1:1; 15-30 ml;H2O from the CuSO4 and sodium ascorbate stock solution) was heated to 50C. After complete consumption of the starting material as judged by TLC, the reaction mixture was allowed to cool to room temperature, was diluted with water (8 ml) and the aqueous layer was extracted with CH2Cl2(3 × 8 ml). The combined organic layers were washed with 25% aq. ammonia (3 × 8 ml) and brine(8 ml). The organic layer was dried over Na2SO4, filtered and the solvent was removed under reduced pressure. Purification by columnchromatography gave the desired products.
  • 33
  • [ 769-26-6 ]
  • [ 121714-18-9 ]
  • [ 1415344-19-2 ]
YieldReaction ConditionsOperation in experiment
68% EXAMPLE 2 9-(2,4,6-trimethylphenyl)-3,6-dihydroxyxanthene (1b). Mesitylacetylene (288 mg, 2 mmol) was dissolved in dry toluene (4 mL) under argon. Butyllithium (700 μL of 2.5 M solution in hexanes, 1.4 mmol) was slowly added via syringe during vigorous stirring. The mixture was stirred for 20 min at room temperature, and then added to a solution of 3,6-bis(dimethyl-tert-butylsilyloxy)xanth-9-one (456 mg, 1 mmol) in toluene (4 mL). The reaction was stirred for 4 hours at 60 C., cooled, and evaporated in vacuum. The residue was dissolved in THF (6 mL), and triethylamine trihydrofluoride (2454, 1.5 mmol) was added. The mixture was stirred for 30 minutes, and evaporated. The residue was dissolved in CHCl3-MeOH (10:1), and subjected to column chromatography on silica gel (eluent 10% MeOH and 1% AcOH in CHCl3 to 10% AcOH and 40% MeOH in CHCl3). Fractions containing title compound were pooled, and evaporated. The residue was co-evaporated with ether (2*50 mL), and dried in vacuum to give 240 mg (68%) of pure title compound as black crystalls. Rf 0.21 (15% MeOH in CHCl3).
  • 34
  • [ 1079889-18-1 ]
  • [ 769-26-6 ]
  • [ 1415344-20-5 ]
YieldReaction ConditionsOperation in experiment
85% EXAMPLE 3 9-(2,4,6-trimethylphenyl)-3,6-dimorpholinoxanthenium chloride (8c). Mesitylacetylene (288 mg, 2 mmol), and N,N,N', N'-tetramethylethylenediamine (210 μL, 1.4 mmol) were dissolved in dry toluene (4 mL) under argon. Butyllithium (700 μL of 2.5 M solution in hexanes, 1.4 mmol) was slowly added via syringe during vigorous stirring. The mixture was stirred for 20 min at room temperature, and solid 3,6-bis(N-morpholino)xanth-9-one (366 mg, 1 mmol). The reaction was stirred for 4 hours at 70 C., cooled, and poured into a mixture of 30 mL ethanol, 20 mL of water, and 1 mL of 10 M aqueous HCl. The mixture was cooled to -20 C. The title compound precipitated and was filtered off to give 450 mg (85%) of pure title compound as dark purple crystals.
  • 35
  • [ 769-26-6 ]
  • [ 1321605-71-3 ]
  • [ 1427459-82-2 ]
YieldReaction ConditionsOperation in experiment
66% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; In tetrahydrofuran; at 60℃; for 12h;Inert atmosphere; General procedure: General procedure for synthesis of indeno[2,1-a]phenalene derivaties: A mixture of compound 3 (54.48 mg, 0.12 mmol), Pd(PPh3)2Cl2 (4.21 mg, 0.006 mmol), CuI (2.30 mg, 0.012 mmol), PPh3 (3.15 mg, 0.012 mmol) and arylacetylene (0.36 mmol) was dissolved in 10 mL of Et3N and 10 mL of THF. The reaction mixture was degassed and stirred at 60 C for 12 h under a N2 atmosphere. The solvent was removed under reduced pressure, and the residue was extracted with CH2Cl2. The organic layer was washed with water and then brine, dried over anhydrous Na2SO4, and then evaporated in vacuum to dryness. The residue was purified by silica gel column chromatography with petroleum ether/chloroform (30:1, v/v) as an eluent to give the target compounds.
 

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