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CAS No. : | 2622-14-2 | MDL No. : | MFCD00003853 |
Formula : | C18H33P | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WLPUWLXVBWGYMZ-UHFFFAOYSA-N |
M.W : | 280.43 | Pubchem ID : | 75806 |
Synonyms : |
|
Num. heavy atoms : | 19 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 90.27 |
TPSA : | 13.59 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.2 cm/s |
Log Po/w (iLOGP) : | 4.08 |
Log Po/w (XLOGP3) : | 5.37 |
Log Po/w (WLOGP) : | 6.47 |
Log Po/w (MLOGP) : | 5.61 |
Log Po/w (SILICOS-IT) : | 5.8 |
Consensus Log Po/w : | 5.47 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.76 |
Solubility : | 0.00483 mg/ml ; 0.0000172 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -5.41 |
Solubility : | 0.00109 mg/ml ; 0.0000039 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -4.3 |
Solubility : | 0.0142 mg/ml ; 0.0000505 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 4.25 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With triethylamine In acetonitrile | d) 5-Carbomethoxy-1,2-dihydro-9H-carbazol-4(3H)-one A suspension of 3-(3-carbomethoxy-2-chloroanilino)cyclohex-2-en-1-one (10.22 g, 36.67 mM), palladium acetate (0.82 g, 3.66 mM), tricyclohexylphosphine (4.10 g, 14.62 mM), and triethylamine (30.0 mL, 21.78 g, 215.2 mM) in 100 mL acetonitrile was heated at 130° C. in a sealed vessel for 14 days. The mixture was diluted with ethyl acetate, washed twice with 1 N HCl, twice with H2O, once with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated to afford 9.9 g of a light brown gum. Purification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate) afforded 4.68 g (52percent) of the 5-carbomethoxy-1,2-dihydro-9H-carbazol-4(3H)-one as a yellow solid. 1H NMR (CDCl3) δ 9.15 (br s, 1H), 7.4 (dd, 1H, J=1 and 8 Hz), 7.35 (dd, 1H, J=1 and 8 Hz), 7.25 (t, 1H, J=8 Hz), 4.05 (s, 3H), 2.95 (t, 2H, J=6 Hz), 2.55 (t, 2H, J=6 Hz), and 2.2 (m, 2H). IR (CHCl3, cm-1) 3400, 3200 (br), 3000, 2950, 1721, 1646, 1466, 1439, 1427, 1299, 1284, 1165, and 1135. MS (ES) m/e 242, 244. Elemental Analyses for C14H13NO3: Calculated: C, 69.12; H, 5.39; N, 5.76. Found: C, 68.82; H, 5.67; N, 5.60. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With water; Selectfluor; In acetonitrile; at 20℃; for 0.166667h; | General procedure: To a solution of 1 (0.2 mmol) in 2 mL of CH3CN/H2O(v/v = 100/1) was added Selectfluor (71 mg, 0.2 mmol). The mixture was stirred at room temperature for 5-60minutes. After removal of the solvent, the residue was then purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate to give the desired product 2. |
98% | With 4-phenylthioxanthone; In methanol; at 20℃; under 760.051 Torr; for 1h;Irradiation; | General procedure: 1a (70.5 mg, 0.20 mmol), 4-phenylthioxanthone (3 mg, 0.01 mmol), CH3OH (30 mL) were added to a pyrex reaction flash which was equipped with a magnetic stirrer. The mixture was irradiated by a 23 W household lamp at rt under air atmosphere. The photoreaction was completed after 40 minutes as monitored by TLC (eluent: petroleum ether). The solvent was removed and the residue was purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate = 10/1?EA) to afford 2a as a solid (74 mg, 100%); 1H NMR (400 MHz, CDCl3) delta 7.56 (dd, J = 11.6, 8.8 Hz, 6 H), 6.95 (dd, J = 8.8, 2.0 Hz, 6 H), 3.83 (s, 9 H). |
With pyridine N-oxide; In acetonitrile; at 110℃; for 24h;Sealed tube; Inert atmosphere; Glovebox; | General procedure: Reactions for each substrate were run in triplicate. For substrate oxidation reactions, either 21 mg pyridine-N-oxide (220 mumol) or 27 mg of x-PVP-N-oxide (220 mumol) was added to 100 mumol of substrate in 500 muL of acetonitrile in a J-Young NMR tube and sealed in the glovebox. The reactions were taken out of the glovebox and heated at 110 C for 24 hours. After cooling to room temperature, the solvent was transferred to a clean vial and 100 muL of a 0.333 M of 2-adamantanone solution in chloroform was added as an internal standard. The solution volume was diluted to 2.0 mL with chloroform, filtered, and analyzed by GC/FID. Product peaks were identified by comparison to GC/FID chromatograms of authentic samples of the expected products, and percent conversions were determined by comparison to 2-adamantanone as a standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane-d2; at 20℃; for 2h;NMR tube;Reactivity; | In a dry box, a Teflon-sealed n.m.r. tube was charged with (2S)-methyl 2-N-acetylaminopenta-2,4-dienoate 57 (10.8 mg, 63.9 mumol), Grubbs' catalyst (50.7 mg, 61.6 mumol) and degassed deuterated DCM (CD2Cl2, 0.8 mL) at room temperature. The n.m.r. tube was shaken gently and reaction progress was monitored by 1H and 31P n.m.r. spectroscopy. Compounds were identified by the following diagnostic resonances: 1H n.m.r. (300 MHz, CD2Cl2): After 15 min: Grubbs' catalyst: delta 8.61 (d, J=7.6 Hz, 2H, ortho-Arom CH), 20.05 (s, 1H, [Ru]CHPh); Ruthenium-dienamide complex 73: delta 7.96 (d, J=11.0 Hz, 1H, [Ru]CHCH), 20.11 (d, J=11.0 Hz, 1H, [Ru]CH); Ruthenium-dienamide chelate 74 (trace): delta 15.20 (d, J=4.2 Hz, 1H, [Ru]CH); Ratio of ruthenium complexes [Ru]CHPh: 73: 74=1.0:1.0:<0.1. After 60 min: Grubbs' catalyst: delta 8.45 (d, J=7.6 Hz, 2H, ortho-Arom CH), 20.04 (s, 1H, [Ru]CHPh); Ruthenium-dienamide complex 73: delta 7.96 (d, J=11.0 Hz, 1H, [Ru]CH=CH), 20.10 (d, J=11.0 Hz, 1H, [Ru]CH); Ruthenium-dienamide chelate 74: delta 6.73 (d, J=3.0 Hz, 1H, [Ru]CHCH), 15.19 (d, J=4.2 Hz, 1H, [Ru]CH); Ratio of ruthenium complexes [Ru]CHPh: 73: 74=3:1:1. After 120 min (no change after 18 h): Ruthenium-dienamide chelate 74: delta 6.71 (d, J=3.0 Hz, 1H, [Ru]CHCH), 15.19 (d, J=4.0 Hz, 1H, [Ru]CH). 31P n.m.r. (300 MHz, CDCl3): delta Ruthenium-dienamide chelate 74: 35.0; Grubbs' catalyst: 37.0; Ruthenium-dienamide complex 73: 38.8; Tricyclohexylphosphine oxide: 46.5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; sodium t-butanolate; In tetrahydrofuran; ethylene glycol; | Example 12 3-[1,3]DIOXOLAN-2-YLIDENE-3H-INDENE-1-CARBONITRILE A solution of tricyclohexylphosphine (536 mg, 1.91 mmol) in tetrahydrofuran (25 mL) was charged with palladium (II) acetate (287 mg, 1.27 mmol) under nitrogen. After 1 hour the reaction mixture was cooled to 0 C. and charged with sodium tert-butoxide (31.6 g, 319 mmol). After 5 minutes a solution of 2-bromo-phenylacetonitrile (25.0 g, 128 mmol) and beta-ethoxyacrylic acid ethyl ester (18.4 mL, 128 mmol) in tetrahydrofuran (75 mL) was added dropwise over 15 minutes. The reaction was heated to 60 C. After 2 hours 30 minutes the reaction mixture was cooled to room temperature and charged with ethylene glycol (200 mL) over 5 minutes and then charged with sulfuric acid (18.8 M, 36 mL) added dropwise over 15 minutes. After 15 hours the reaction was diluted with water (90 ml) and a solid product was filtered through a glass frit. The solid was dried under vacuum affording 3-[1,3]dioxolan-2-ylidene-3H-indene-1-carbonitrile (21.6 g, 102 mmol, 80%) as a light tan solid. The crude material was slurried in isopropanol (50 mL) for 2 hours, filtered and dried under vacuum affording 3-[1,3]dioxolan-2-ylidene-3H-indene-1-carbonitrile (20.8 g, 98.5 mmol, 77%) as a light tan solid. 1H NMR (400 MHz, d6-DMSO) delta7.75 (s, 1H), 7.74 (d, 1H, J=7.9), 7.50 (d, 1H, J=7.1), 7.22 (m, 2H), 4.97 (t, 2H, J=7.8), 4.85 (t, 2H, J=7.8); 13C NMR (100 MHz, d6-DMSO) 167.4, 136.7, 135.7, 133.1, 124.7, 123.9, 121.1, 119.4, 118.1, 97.8, 92.7, 71.1, 69.9; mp (decomposition) 228 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium chloride; sodium t-butanolate; In 1,2-dimethoxyethane; | Example 5 3-(ETHOXY-HYDROXY-METHYLENE)-3H-INDENE-1-CARBONITRILE, SODIUM SALT A solution of tricyclohexylphosphine (21.5 mg, 0.0770 mmol) in ethylene glycol dimethyl ether (10 mL) under nitrogen was charged with palladium (II) acetate (11.5 mg, 0.0510 mmol). The reaction was stirred at room temperature until the solution was homogenous (approx. 15 minutes), cooled to 0° C. and charged with sodium tert-butoxide (2.53 g, 25.5 mmol). After 5 minutes a solution of 2-bromo-phenylacetonitrile (1.32 mL, 10.2 mmol) and ethyl-3-ethoxyacrylate (1.47 mL, 10.2 mmol) in ethylene glycol dimethyl ether (10 ml) was added dropwise over 10 minutes. Upon complete addition, the reaction was warmed to room temperature then heated to 85° C. for 1 hour. The reaction was cooled to room temperature then diluted with ethyl acetate (50 mL) and poured into aqueous potassium dihydrogen phosphate (0.25 M, 50 mL), pH=7. The aqueous layer was saturated by addition of sodium chloride as solid and the organic layer separated and washed with aqueous saturated sodium chloride (1*50 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo affording 3-(ethoxy-hydroxy-methylene)-3H-indene-1-carbonitrile, sodium salt, as a dark brown oil (1.74 g, 84percent) which solidifies on standing. 1H NMR (400 MHz, CD3CN) delta8.04 (d, 1H, J=6.0), 7.58 (s, 1H), 7.43 (d, 1H, J=6.0), 6.98-6.91 (m, 2H), 4.25 (q, 2H, J=7.2), 1.35 (t, 3H, J=7.2); 13C NMR (100 MHz, CD3CN) delta166.7, 135.5, 132.3, 131.3, 122.8, 120.5, 119.0, 118.4, 117.7, 103.3, 79.2, 58.2, 14.6; IR (ATR, neat) 2176, 1597, 1465, 1257, 1195,1068, 1029, 754 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium chloride; sodium t-butanolate; In 1,2-dimethoxyethane; | Example 6 3-(ETHOXY-HYDROXY-METHYLENE)-3H-INDENE-1-CARBONITRILE, SODIUM SALT A solution of tricyclohexylphosphine (204 mg, 0.720 mmol) in ethylene glycol dimethyl ether (10 mL) under nitrogen was charged with palladium (II) acetate (148 mg, 0.660 mmol). The reaction was stirred at room temperature until the solution was homogenous (approx. 25 minutes), cooled to 0 C. and charged with sodium tert-butoxide (1.63g, 16.6 mmol). After 10 minutes a solution of 2-chlorophenylacetonitrile (1.00 g, 6.60 mmol) and ethyl-3-transethoxyacrylate (953 muL, 6.60 mmol) in ethylene glycol dimethyl ether (10 ml) was added dropwise over 5 minutes. Upon complete addition, the reaction was warmed to room temperature and then heated to 85 C. for 22 hours. The reaction was cooled to room temperature then diluted with methyl tert-butyl ether (30 mL) and poured into aqueous potassium dihydrogenphosphate (0.25 M, 40 mL), pH=7. The aqueous layer was separated then saturated by addition of solid sodium chloride and extracted with ethyl acetate (1*50 mL). The organic layer was separated and washed with aqueous saturated sodium chloride (2*30 mL), dried over sodium sulfate, filtered and concentrated in vacuo affording 3-(ethoxy-hydroxy-methylene)-3H-indene-1-carbonitrile, sodium salt, as a light orange oil (1.06 g, 5.0 mmol, 75 %). For physical data see Example 5 above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium chloride; sodium t-butanolate; In 1,2-dimethoxyethane; | Example 7 3-(ETHOXY-HYDROXY-METHYLENE)-5,6-DIMETHOXY-3H-INDENE-1-CARBONITRILE, SODIUM SALT A solution of tricyclohexylphosphine (82.0 mg, 0.293 mmol) in ethylene glycol dimethyl ether (10 mL) under nitrogen was charged with palladium (II) acetate (43.7 mg, 0.195 mmol). The reaction was stirred at room temperature until the solution was homogeneous (approx. 15 minutes) and stirred an additional 5 minutes before cooling to 0° C. and charging with sodium tert-butoxide (996 mg, 9.75 mmol). After 5 minutes a solution of <strong>[51655-39-1]2-bromo-4,5-dimethoxyphenylacetonitrile</strong> (1.00 g, 3.90 mmol) and ethyl-3-ethoxyacrylate (0.564 ml, 3.90 mmol) in ethylene glycol dimethyl ether (5 ml) was added dropwise over 10 minutes. Upon complete addition the reaction mixture was warmed to room temperature and then heated to 85° C. for 16 hours. The reaction was cooled to room temperature then diluted with methyl tert-butyl ether (50 mL) and poured into aqueous potassium dihydrogenphosphate (0.25 M, 100 mL). The aqueous layer was separated and solid sodium chloride was added to the aqueous layer until saturated. The aqueous layer was extracted with ethyl acetate (1*125 mL) and this organic layer was washed with aqueous saturated sodium chloride 12*35 ml), dried over sodium sulfate, filtered and concentrated in vacuo affording 3-(ethoxy-hydroxy-methylene)-5,6-dimethoxy-3H-indene-1-carbonitrile, sodium salt, as a dark brown oil (906 mg, 3.3 mmol, 85 percent) which crystallized on standing. 1H NMR (400 MHz, d4-MeOH) delta7.64 (s, 1H), 7.46 (s, 1H), 6.99 (s, 1H), 4.56 (q, 2H, J=7.1), 3.86 (s, 6H), 1.38 (t, 3H, J=7.05); 13C NMR (100 MHz,d4-MeOH) delta167.8, 145.0, 144.5, 130.2, 129.4, 126.4, 123.3, 112.5, 104.0, 102.6, 100.7, 79.0, 58.4, 55.6, 14.1; IR (ATR, neat) 3499, 2164, 1629, 1482, 1449, 1282, 1207, 1157, 1124, 1076, 845, 769 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.68 g (52%) | With triethylamine;palladium diacetate; In acetonitrile; | d) 5-Carbomethoxy-1,2-dihydro-9H-carbazol-4(3H)-one A suspension of 3-(3-carbomethoxy-2-chloroanilino)cyclohex-2-en-1-one (10.22 g, 36.67 mM), palladium acetate (0.82 g, 3.66 mM), tricyclohexylphosphine (4.10 g, 14.62 mM), and triethylamine (30.0 mL, 21.78 g, 215.2 mM) in 100 mL acetonitrile was heated at 130 C. in a sealed vessel for 14 days. The mixture was diluted with ethyl acetate, washed twice with 1 N HCl, twice with H2O, once with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated to afford 9.9 g of a light brown gum. Purification by HPLC on silica gel (elution with gradient methylene chloride/ethyl acetate) afforded 4.68 g (52%) of the 5-carbomethoxy-1,2-dihydro-9H-carbazol-4(3H)-one as a yellow solid. 1H NMR (CDCl3) delta 9.15 (br s, 1H), 7.4 (dd, 1H, J=1 and 8 Hz), 7.35 (dd, 1H, J=1 and 8 Hz), 7.25 (t, 1H, J=8 Hz), 4.05 (s, 3H), 2.95 (t, 2H, J=6 Hz), 2.55 (t, 2H, J=6 Hz), and 2.2 (m, 2H). IR (CHCl3, cm-1) 3400, 3200 (br), 3000, 2950, 1721, 1646, 1466, 1439, 1427, 1299, 1284, 1165, and 1135. MS (ES) m/e 242, 244. Elemental Analyses for C14H13NO3: Calculated: C, 69.12; H, 5.39; N, 5.76. Found: C, 68.82; H, 5.67; N, 5.60. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; methanol; dichloromethane; water; | EXAMPLE 21 Tert-butyl 4-[4-[6-amino-5-(1,3-benzoxazol-2-yl)-3-pyridyl]-3-methyl-pyrazol-1-yl]piperidine-1-carboxylate A mixture of 3-(1,3-benzoxazol-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amine (600 mg), <strong>[1092500-89-4]tert-butyl 4-(4-bromo-3-methyl-pyrazol-1-yl)piperidine-1-carboxylate</strong> (557 mg), tris(dibenzylideneacetone)dipalladium (74.1 mg), tricyclohexylphosphine (45.4 mg) and potassium phosphate (584 mg) in 1,4-dioxane (3.4 mL) and water (0.4 mL) was degassed with argon, then stirred at 100 C. for 3 h under argon. Solvents were removed. The crude product was adsorbed on silica gel and purified by flash chromatography on silica gel eluding with 5 to 10% methanol in dichloromethane. The solvent was evaporated to dryness to afford tert-butyl 4-[4-[6-amino-5-(1,3-benzoxazol-2-yl)-3-pyridyl]-3-methyl-pyrazol-1-yl]piperidine-1-carboxylate (500 mg); NMR Spectrum: (DMSOd6) 1.43 (s, 9H), 1.78 (dd, 1H), 1.83 (dd, 1H), 1.99-2.07 (m, 2H), 2.33 (s, 3H), 2.91 (bs, 2H), 4.01-4.11 (m, 2H), 4.24-4.32 (m, 1H), 7.42-7.50 (m, 2H), 7.65 (bs, 2H), 7.77-7.83 (m, 2H), 8.10 (s, 1H), 8.29 (d, 1H), 8.35 (d, 1H); Mass spectrum: M+H+: 475 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium acetate; In 1,4-dioxane; | Step 3. Preparation 2-chloro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (SM-9) To a glass pressure vessel was added <strong>[56131-46-5]3-bromo-2-chloroaniline</strong> (3.08 g, 14.9 mmol), bis(pinacolato)diboron (4.55 g, 17.9 mmol), tricyclohexylphosphine (0.29 g, 1.04 mmol), potassium acetate (2.2 g, 22.4 mmol), and Pd2 dba3 (0.41 g, 0.45 mmol) in 1,4-dioxane (75 mL) to give a red suspension which was sparged with nitrogen, and the reaction vessel was then sealed. The reaction was heated in an oil bath to 120° C. for 2 hours. LCMS of an aliquot indicted complete conversion and the reaction was allowed to cool to room temperature. SiliaBond DMT (4 g from SiliCycle) was added and the resulting mixture was stirred at room temperature for 30 minutes, then filtered through a plug of neutral alumina layered with SiO2. The filter cake was washed thoroughly with EtOAc and the combined filtrates were partitioned water. The phases were separated and the aqueous portion was extracted with EtOAc. The combined organic portions were washed with water (2*), brine, dried (Na2SO4), and concentrated to provide 2-chloro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (1.6 g) as a dark yellow crystalline solid which was used without further purification: LCMS(m/z) 254.0 (MH+); tR=0.91 minute. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium acetate;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; | Step 2. Preparation of 2,5-difluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline To a solution of 3-bromo-2,5-difluoroaniline (2.0 g, 9.4 mmol), bis(pinacolato)diboron (2.86 g, 11.25 mmol), tricyclohexylphosphine (0.184 g, 0.656 mmol), and potassium acetate (1.380 g, 14.06 mmol) in 1,4 dioxane (1.0 ml), was added Pd2(dba)3 (0.26 g, 0.28 mmol) and the resulting reaction mixture was irradiated to 120 C. in the microwave for 30 minutes. The reaction was allowed to cool to room temperature and was diluted with EtOAc and the reaction was diluted with EtOAc and palladium scavenger (Silicycle DMT) was added and mixture was stirred for 30 minutes, then filtered through a sintered funnel. The filtrate was washed with water, brine, dried (MgSO4), and concentrated to afford filtered and stripped to 2,5-difluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (2.4 g, 9.4 mmol): LCMS(m/z) 255.1 (MH+), tR=0.95 minute; LCMS(m/z) 174.0 (MH+, boronic acid), tR=0.3 minute. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | b) A brown suspension of RuCl2(1,5-cyclooctadiene) (560 mg; 2 mmol), 0.6 ml of 1,8-diazobicyclo[5.4.0]undec-7-ene (DBU) and 1.18 g of tricyclohexylphosphine in 60 ml of isopropanol was stirred at 80 C. for 2 hours. 60 ml of toluene was added to the resulting brick-red suspension and the mixture was stirred at 80 C. for a further 90 minutes and cooled to -10 C. After addition of 0.55 ml of trimethylsilylacetylene, 10 ml of 2 M HCl solution in diethyl ether were added and the mixture was subsequently stirred for 5 minutes. The mixture was warmed while stirring to 0 C. and stirred for 45 minutes. After evaporation at 0 C. in a high vacuum, the residue was stirred with cold MeOH. The resulting violet powder was washed with cold methanol and dried under reduced pressure. Yield 1.40 g (92%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 2; Synthesis of the Alkylidene Complex (2): Ru(cod)Cl2 (660 mg, 2.35 mmol) was suspended in iPrOH (20 ml) under an Ar atmosphere. DBU (0.75 ml) and PCy3 solution (c=20%, 0.77 M in toluene, 7.7 ml) was added. The brown suspension obtained was stirred at 80 C. for 1 hour and toluene (25 ml) was then added. The mixture was stirred at 80 C. for a further 30 minutes. The reaction mixture was then cooled to 0 C. and 1-trimethylsilyl-1-hexyne (2.1 g) was added. After stirring for 10 minutes, HCl solution (c=2 M in Et2O, 2.4 ml) was added to the reaction mixture at 0 C. After stirring for 1 hour, the reaction mixture was evaporated. MeOH (about 30 ml) was added to the residue. Filtration gave the complex 2. The NMR also shows by-products.NMR in CDCl3 delta 31P 35.81 ppm. 1H delta 20.01 ppm. |
Yield | Reaction Conditions | Operation in experiment |
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58% | With sodium bicarbonate; caesium carbonate;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; dichloromethane; water; toluene; | Step 1: Synthesis of 4-chloro-5-methyl-6-(2-methylphenyl)pyrimidine First, into a recovery flask equipped with a reflux pipe were put 5.0 g of <strong>[4316-97-6]4,6-dichloro-5-methylpyrimidine</strong>, 4.6 g of 2-methylphenylboronic acid, 20 g of cesium carbonate, 2.5 mL of 15% toluene solution of tricyclohexylphosphine (abbreviation: Cy3P), 0.47 g of tris(dibenzylideneacetone)dipalladium(0) (abbreviation: Pd2(dba)3), and 40 mL of dioxane, and the air in the flask was replaced with argon. This reaction container was heated by irradiation with microwaves (2.45 GHz, 150 W) for 2 hours. After that, water was added to this solution and an organic layer was extracted with dichloromethane. The obtained organic layer was washed with saturated aqueous solution of sodium hydrogen carbonate, water, and saturated saline, and was dried with magnesium sulfate. The solution after drying was filtered. The solvent of this solution was distilled off, and then the obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent and the obtained fraction was concentrated, so that 4-chloro-5-methyl-6-(2-methylphenyl)pyrimidine was obtained (a white solid, yield of 58%). Note that the irradiation with microwaves was performed using a microwave synthesis system (Discover, manufactured by CEM Corporation). A synthesis scheme (q-1) of Step 1 is shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With indium(III) bromide; 1,1,3,3-Tetramethyldisiloxane; In toluene; at 100℃; for 30h;Inert atmosphere; Sealed tube; | General procedure: In a sealed tube containing a solution of the phosphine oxide derivative (5 mmol) in anhydrous toluene (1 M) was added InBr3 (1 mol %, 0.05 mmol) and the TMDS (1.5 equiv, 7.5 mmol) under an argon atmosphere. The reaction mixture was stirred at 100 C during 7-40 h depending on the substrate (the reaction was monitored by 31P NMR). After complete consumption of the reagent the mixture was kept under argon in the sealed tube and cooled to 0 C. A solution of BH3.SMe2 (2 M in THF, 1 equiv) was then slowly added. After 1 h at room temperature, 31P NMR analysis of an aliquot indicates complete conversion to phosphine borane adduct. The crude was poured in an erlenmeyer flask and silica gel was carefully added while stirring. When silica gel was added in the reaction mixture, a slightly exothermic reaction was observed. The reaction mixture was then filtered on silica gel and washed several times with ethyl acetate. After evaporation of the ethyl acetate, the residue was purified by flash chromatography on silica gel with pure cyclohexane to afford the desired phosphine-borane. | |
95%Chromat. | With [AlH3(triethylamine)]; In hexane; at 20℃; for 0.166667h;Inert atmosphere; Schlenk technique; | General procedure: Triphenylphosphine oxide or sulfide (1 mmol), dry hexane (1 mL), and Ic (1 mmol) were added to a Schlenk tube under the atmosphere of nitrogen. The reaction was carried out at room temperature for 10 min and monitored by TLC. Upon completion of the process the reaction mixture was filtered by silica gel and washed several times with ethyl acetate. Ethyl acetate was evaporated and the residue purified by flash chromatography on silica gel with pure cyclohexane toafford the desired phosphine. The yield was determined by GC without additional purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,2-dimethoxyethane; at 80℃; for 3.5h;Inert atmosphere; Schlenk technique; Sealed tube; | [0169] Under argon atmosphere, acetylacetonato iridium (1,5-cyclooctadiene) (40 mg, 0.1 mmol) and tricyclohexylphosphine (d) (56 mg, 0.2 mmol) were placed in a Schlenk flask. After addition of a degassed 1,2-dimethoxyethane (2 mL) thereto with a syringe, the flask was tightly sealed, and the mixture was stirred at 80 C. for 3.5 hours. Thereafter, 1,2-dimethoxyethane was removed under reduced pressure, to obtain the iridium complex D as viscous brown solids. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | General procedure: AgNO3 0.017g (0.1mmol) was dissolved in mixture of acetonitrile/ methanol (2:3) (20mL) and L1 0.018g (0.2mmol) was added. The mixture was stirred mechanically for 1h at 50C. The reaction mixture was further treated with triphenyl phosphine (P1) 0.028g (0.1mmol) in 5ml chloroform and stirring was continued for another 30min. The second step results in solubilisation of the precipitates obtained in the first step. The colorless solution obtained was filtered to avoid any impurity and kept undisturbed for crystallization by slow evaporation at room temperature. After three days colorless block-like crystals were obtained. Yield 0.054g, 88%. Anal. Calc. for C40H52Ag2N14O7P2S4: C, 38.5; H, 4.2; N, 15.7. Found: C, 38.4; H, 4.1; N, 15.7%. IR cm-1: 3477 (m), 3413 (m), 3040 (s), 1987 (w), 1633 (s), 1633 (s), 1434 (s), 1359 (s), 1156 (m), 1093 (s), 997 (ms), 827 (m), 751 (m), 695 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | General procedure: AgPF6 0.025g (0.1mmol) was dissolve in acteonitrile (15ml) and tricyclohexyl phosphine (P2) in (10ml) chloroform was added. The reaction mixture was stirred mechanically for 30min at 30C. To this clear solution was added 0.018g (0.2mmol) of thiosemicarbazide (L1). The reaction mixture was stirred for another 30min at 50C. The colorless clear solution obtained was filtered to avoid any impurity and kept at room temperature for slow evaporation. After a couple of days crystalline product was obtained. Yield 0.061g, 86%. Anal. Calc. for C20H43AgF6N6P2S2: C, 33.5; H, 6.0; N, 11.7. Found: C, 33.6; H, 6.1; N, 11.7%. IR cm-1: 3465 (m), 3412 (m), 3117 (s), 2925 (s), 2849 (s), 1637 (s), 1612 (s), 1456 (s), 1373 (s), 1115 (m), 1076 (s), 981 (ms), 812 (m), 745 (m), 697 (s), 505 (m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In tetrahydrofuran; at 40 - 65℃; for 1h;Inert atmosphere; | EXAMPLE 2 Preparation of dichloro(3-phenyl-1H-inden-1-ylidene)bis-(tricyclohexylphosphine)ruthenium(II) (according to the invention; c = 0.5 mol/l) A one liter glass reactor with condenser and stirrer is filled with argon and thereafter with 500 ml of THF. The solvent is warmed up to 40C. Then 221.7 g (250 mmol, 1 eq.) of (PPh3)2Cl2Ru(3-phenylindenylidene) (Umicore AG & Co. KG, Hanau) and 155 g (98.1% purity, 540 mmol, 2.16 eq.) of tricyclohexylphosphine (PCy3, Aldrich) are added successively with stirring. The reaction mixture is stirred under reflux (65C) for 1 h during which time the product precipitates in form of dark red crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium; In tetrahydrofuran; hexane; at -78 - 20℃; for 4h;Inert atmosphere; | Ru(PPh3)3HC1 (0.100 g, 0.108 mmol), thioacetal 27 (0.030 g, 0.130 mmol) and PCy3 (0.045 g, 0.162 mmol) were dissolved in THF (5 mL) and toluene (5 mL) under N2. The solution was cooled to -78C and n-BuLi (0.068 mL, 1.6 M in hexanes) was added dropwise. The reaction mixture was stirred at - 78C for 2 h and then allowed to warm to room temperature. After stirring at room temperature foranother 2 h the solvent was pumped off The resulting brown solid was dissolved in toluene (10 mL) and filtered through a plug of celite. The filtrate was concentrated and hexanes (20 mL) was added to precipitate 1 which was collected by filtration and washed with hexanes (3 x 5 mL) to give a red solid. All spectral data matched that of compound 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; methanol; hexane; dichloromethane; water; ethyl acetate; | Synthesis of 4-(biphenyl-4-yl)-1H-pyrazole 10 <strong>[95162-14-4]4-Bromo-1-trityl-1H-pyrazole</strong> (970 mg, 3.35 mmol, 1.0 eq), biphenyl-4-ylboronic acid (796 mg, 4.02 mmol, 1.2 eq), Pd2(dba)3 (123 mg, 0.134 mmol, 0.04 eq), PCy3 (90 mg, 0.322 mmol, 0.096 eq) and K3PO4 (1210 mg, 5.70 mmol, 1.7 eq) were added to a dry pressure tube equipped with a magnetic stir bar. Then the tube was evacuated and backfilled with nitrogen, this evacuation and backfill procedure was repeated twice. Solvent dioxane (21 mL) and H2O (9 mL) were added under nitrogen. The mixture was stirred in an oil bath at a temperature of 95-105 C. for 24 hours. Then the mixture was cooled to ambient temperature, the precipitate was filtered off and washed with ethyl acetate, dried in air to obtain a brown solid 1053 mg which was used directly for the next step. A mixture of the brown solid (1053 mg) in MeOH (32 mL)/H2O (27 mL)/HCl (5 mL) was stirred at 40-45 C. for 4 hours, cooled. The organic solvent was removed under reduced pressure. The precipitate was filtered off and washed with water for twice, dried in air. The collected solid was purified through flash column chromatography on silica gel using hexane/ethyl acetate (3:1) first, then dichloromethane/methanol (10:1) as eluent to afford the desired product 4-(biphenyl-4-yl)-1H-pyrazole 10 as a brown solid 430 mg in 58% total yield for the two steps. 1H NMR (DMSO-d6, 400 MHz): delta 7.36 (t, J=7.6 Hz, 1H), 7.47 (t, J=8.0 Hz, 2H), 7.65-7.72 (m, 6H), 7.98 (bs, 1H), 8.25 (bs, 1H), 12.97 (bs, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | In toluene; at 115℃; for 48h; | A mixture of [RuCl2(COD)]n (309 mg, 1.103 mmol), PCy3 (309 mg, 1.103 mmol) and la (294 mg, 1.103 mmol) was stirred in toluene (10 ml) at 115 C for 48 h in a KONTES pressure tube. After cooling down, the brick colored precipitate was collected on a filter frit, washed with Et20 (3 x 10 ml) and vacuum dried to afford 642 mg of the crude material. To the crude material was added CH2C12 (~ 32 ml) and the obtained mixture was brought to reflux and filtered using a Whatman syringe filter (PTFE membrane, pore size 0.45 muiotaeta). Layering the obtained red-brown solution with Et20 (125 ml) afforded 327 mg (41%) of the product as a pink-brown powder after 5 days. Elem. Anal.: Calcd for C32H55Cl2N2OPRuS (718.81): C, 53.47; H, 7.71; N, 3.90%. Found: C, 53.11; H, 8.00; N, 3.86%. 31P{1H} (162 MHz, CD2C12, r.t.): delta 24.0 (s). 1H NMR (400 MHz, CD2C12, r.t.): delta 0.09 (brs, 1H), 0.92 (brs, 2H), 1.04-1.63 (m, 15H), 1.63-2.05 (m, 9H), 2.10-2.45 (brs, 3H), 2.45-2.70 (brs, 1H), 2.83-3.28 (overlapped, 7H), 3.31-3.56 (overlapped, 6H), 3.56-3.90 (overlapped, 4H), 3.98 (t, J~ 8 Hz, 1H), 5.57 (brs, NH, 1H), 7.31 (t, J~ 7 Hz, 2H), 7.38 (t, J~ 6 Hz, 1H), 8.15 (d, J~ 7 Hz, 2H). 13C{1H} selected for the coordinated NNS ligand (100.5 MHz, CD2C12, r.t.): delta 46.6 (s, 1C), 46.8 (s, 1C), 48.3 (s, 1C), 53.9 (s, 1C, overlapped with CD2C12 peak), 54.8 (s, 1C), 60.0 (s, 1C), 60.7 (s, 1C), 61.7 (s, 1C), 128.1 (s, 2Cmeta, Ph), 129.3 (s, Cpam, Ph), 134.9 (s, 2Cortho, Ph), 138.0 (s, Cipso, Ph). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In toluene; at 115℃; for 48h; | A mixture of [RuCl2(COD)]n (309 mg, 1.103 mmol), PCy3 (309 mg, 1.103 mmol) and Id (248 mg, 1.103 mmol) was stirred in toluene (10 ml) at 115 C for 48 h (in a KONTES pressure tube). After cooling, the brick colored precipitate was filtered on a filter frit, washed with Et20 (3 x 10 ml) and partially vacuum dried on the filter (vacuum pump). The residue was extracted from the filter frit with dichloromethane (6 >< 3 ml). The obtained solution was layered with Et20 (100 ml). Red-brown crystals were collected in few days (521 mg, 70%> yield). Elem. Anal: Calcd for (0461) C30H53Cl2N2PRuS (676.77): C, 53.24; H, 7.89; N, 4.14%. Found: C, 53.10; H, 7.95; N, 4.05%. 31P{1H} (162 MHz, CDC13, r.t.): delta 27.0 (s). 1H NMR (400 MHz, CDC13, r.t.): delta 0.78-3.90 (overlapped m, 47H), 5.57 (brs, 1H, NH), 7.22-7.53 (m, 3Eta), 8.10-8.30 (m, 2Eta). 13C{1H} (100.5 MHz, CDC13, r.t., selected without PCy3 carbon atoms): delta 46.7 (s, 1C), 46.8 (s, 1C), 48.5 (s, 1C), 52.3 (s, 1C), 54.2 (s, 1C), 67.2 (s, 1C), 128.2 (s, 2Cmeta, Ph), 129.4 (s, Cpara, Ph), 134.9 (s, 2Cortho, Ph), 137.8 (s, Cipso, Ph). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | To a solution of HOC4F9 (216 μL, 1.55 mmol) in 30 mL Et2O was added 1 equiv Cu(mes) (282.9 mg, 1.55 mmol) which was then allowed to stir for 40 min. One equiv of P(cy)3 was added as a solid (434.1 mg, 1.55 mmol) which caused a yellow solid to precipitate. The mixture was filtered and the solid collected over Celite, washed with 16 mL hexanes, and dried under vacuum for 2 h. Crystalline material (402.2 mg, 45% yield) was obtained from a 2 mL CH2Cl2 solution into which hexanes vapors were diffused. Calc. (%). for C22H33OF9PCu: C, 45.64; H, 5.74; F, 29.53. Found (%): C, 46.31; H, 5.80; F, 28.90. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hexamethylsilazane; In benzene; at 90℃; under 1551.49 Torr; for 12h;Schlenk technique; | [Ru(COD)Cl2]n (300 mg, 1 mmol), IMesH2Cl (1.47 g, 4 mmol), tricyclohexylphosphine (300 mg, 1 mmol), and KN(SiMe3)2 (540 mg, 2.5 mmol) were weighed directly into a 600 mL Schlenk tube. The flask was evacuated and filled with dry argon (2×). Degassed benzene (300 mL) was added and the flask was pressurized to 30 psi with H2. The suspension was vigorously stirred for 12 hours at 90 C., yielding a bright yellow solution and white precipitate (1). After cooling the reaction to 5 C., propargyl chloride (0.3 mL, 4 mmol) was slowly added via syringe and the reaction mixture was allowed to warm to room temperature. The resulting brown benzene solution was washed with degassed 1M HCl (2×), degassed brine (2×), filtered through Celite and concentrated in vacuo to afford compound (2) as a brown solid in 90% yield (95% purity). The brown solid displayed catalytic behavior identical with previously synthesized second-generation catalysts. Analytically pure (2) was obtained by column chromatography on silica gel (degassed 3:1 hexanes/Et2O). 1H NMR (CD2Cl2): delta 18.49 (d, J=11.1 Hz, 1H), 7.26 (d, J=10.9 Hz, 1H), 6.97 (s, 2H), 6.77 (s, 2H), 3.92 (m, 4H), 2.58 (s, 6H), 2.37 (s, 6H), 2.29 (s, 3H), 2.23 (s, 3H), 0.88-1.584 (m, 33H), 1.06 (s, 3H), 1.08 (s, 3H). 31P NMR (CD2Cl2): delta 28.9. The reaction was repeated several times with one or more reaction conditions modified so as to optimize the yield of the product. It was found that the yield could be increased to greater than 95% by reducing the reaction temperature from 90 C. to 80 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | Dichloro(1,5-cyclooctadiene)ruthenium (4.0 g, 0.014 moles), tricyclohexylphosphine (8.4 g, 0.030 moles), degassed triethylamine (2 mL), and degassed sec-butanol (60 mL) were combined in a pressure bottle under argon. The pressure bottle was purged with hydrogen gas, pressurized to 60 psi, and the mixture heated to 80 C. for 18 hours (the bottle was repressurized as needed to maintain 60 psi hydrogen). The reaction mixture was then allowed to cool down and the hydrogen gas was vented off. Degassed methanol (60 mL) was added to the orange slurry and the filtrate decanted off via stick filtration under argon to leave an orange solid in the bottle, which was washed with degassed methanol (60 mL). Degassed toluene (60 mL) was added to the orange solid and the orange slurry cooled to 0 C. Degassed 3-chloro-3-methyl-1-butyne (1.7 mL, 0.015 moles) was added dropwise via syringe at 0 C. The orange slurry progressively turned to a maroon slurry, while gas bubbled away. The mixture was stirred at room temperature for 2 hours after addition was complete. Ligand precursor [ 2] (18 g, 0.102 moles) was then charged and the mixture was heated to 80 C. and sparged with argon for 3 days (degassed toluene was added as needed). The brown slurry was allowed to cool to room temperature and a mixture of 30 mL methanol and 10 mL of concentrated hydrochloric acid was added in air with mixing. After stirring for 15 minutes at room temperature, the two phases were allowed to separate and the methanol phase was decanted off. Trituration with methanol (2×50 mL) gave a solid, which was collected on a frit and washed with more methanol (2×20 mL). The brown solid was then washed with hexanes (2×20 mL) and dried to give [ 8] (5.1 g, 0.085 moles) in 61% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In tetrahydrofuran; at 20℃; for 3h;Inert atmosphere; | To a solution of 2-naphthyl triflate (1a; 1.38 g, 5.00 mmol) and LiBr(478 mg, 5.50 mmol) in THF (20 mL) were added PCy3 (4.21 g, 15.0mmol) and Ni(cod)2 (1.38 g, 5.02 mmol) at r.t. After stirring for 2 h at this temperature, the solution was concentrated under reduced pressure. The residue was washed with n-hexane and MeOH to give 6 as ayellow solid; yield: 3.50 g (4.23 mmol, 85%); mp 122 C (dec.). IR (ZnSe): 731, 818, 849, 935, 1003, 1026, 1173, 1202, 1445, 1572,1748, 2845, 2924 cm-1. 1H NMR (C6D6, 400 MHz): δ = 0.85-1.30 (m, 18 H, Haliph), 1.47-1.57(m, 6 H, Haliph), 1.60-1.88 (m, 24 H, Haliph), 2.05-2.23 (m, 18 H, Haliph), 7.13-7.19 (m, 1 H, Harom), 7.29 (dd, J = 8.0, 8.0 Hz, 1 H, Harom), 7.40 (d, J = 8.0 Hz, 1 H, Harom), 7.59 (d, J = 8.0 Hz, 1 H, Harom), 7.65 (d, J = 8.0 Hz,1 H, Harom), 8.05 (s, 1 H, Harom), 8.15 (d, J = 8.0 Hz, 1 H, Harom). 13C{1H} NMR (C6D6, 100 MHz): δ = 27.5 (6 C, 6 CH2), 28.67 (6 C, 6 CH2), 28.71 (6 C, 6 CH2), 31.0 (6 C, 6 CH2), 31.1 (6 C, 6 CH2), 35.4 (t, 1JC-P = 8.7Hz, 6 C, 6 PCH), 123.9 (CH), 124.3 (CH), 126.1 (2 C, 2 CH), 131.3 (C), 133.6 (C), 138.2 (CH), 138.6 (CH), 150.1 (t, 2JC-P = 33.5 Hz, NiC). One signal for aromatic CH carbon overlapped with the solvent peak. 31P{1H} NMR (C6D6, 160 MHz): δ = 11.6 (s). HRMS (ESI+): m/z [M - Br]+ calcd for C46H73NiP2+: 745.4535; found: 745.4520. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | A mixture of ruthenium(III)chloride hydrate (8.05 g ≈0.03 mol) and triphenylphosphane (39.3 g, 0.15 mol) wasplaced in a Schlenk flask, which was purged with argon. Methanol (300 mL) wasadded into the flask and the resulting mixture was heated at reflux for 4 h undercontinuous stirring. After cooling of the reaction mixture to rt, the precipitate wasfiltered off, washed with Et2O (3 × 100 mL) and air-dried to give 30.93 g of theWilkinson complex as black powder.Dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphane)ruthenate(8). A solution of RuCl2(PPh3)3-4 (40.0 g, ≈41.7 mmol) and 1,1-diphenyl-2-propyn-1-ol(10.4 g, 50.1 mmol) in abs. THF (300 mL) was placed into a Schlenk flask under anargon atmosphere. A 5.4 M solution of HCl in dioxane (6.2 mL, 33.4 mmol) wasadded and then the mixture was heated at reflux for 30 min under continuous stirringand an argon atmosphere. After cooling to rt, around 50% of mixture volume wasevaporated under reduced pressure. Acetone (280 mL) and tricyclohexylphosphane25.7 g (91.9 mmol) were added to the residue and the resulting suspension wasstirred until thickening (≈0.5 h). After holding at -20 for 10 h the precipitate wasfiltered off and washed sequentially by methanol (2 × 80 mL), acetone (2 × 100 mL)and hexane (100 mL), then dried under vacuum at rt to give indenylidene-rutheniumcomplex 8 in 94% yield (36.3 g, 39.2 mmol) as red-brown powder.Complex 8 can be obtained by an analogical procedure in 90% yield (34.8 g)using absolute dioxane as a solvent instead absolute THF. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6% | In tetrahydrofuran; for 23h;Irradiation; Inert atmosphere; | General procedure: A solution of [(C5H5)Mn(CO)3] (I) and a slight molar excessof the phosphane in tetrahydrofuran (THF, 120 ml) was irradiatedfor 7 h under argon. The colours of the solutionschanged from yellow to red with concomitant gas evolution.After further stirring for 16 h, the solvent was evacuated andthe residue dissolved in diethyl ether (Et2O) and filteredthrough a plug of silica gel. The solvent was evaporated againand the residue dissolved in the minimum amount of petroleumether. This solution was placed on top of a silica gelchromatography column (alumina in the case of 3a) and theproducts were eluted with a petroleum ether/Et2O (9:1 v/v)mixture. Evaporation of the eluate yielded the products asyellow powders. Recrystallization from petroleum ether (with some added Et2O) by slow evaporation in a refrigerator at5 C yielded crystals of all three compounds. |
Tags: 2622-14-2 synthesis path| 2622-14-2 SDS| 2622-14-2 COA| 2622-14-2 purity| 2622-14-2 application| 2622-14-2 NMR| 2622-14-2 COA| 2622-14-2 structure
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P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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