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CAS No. : | 2845-89-8 | MDL No. : | MFCD00000591 |
Formula : | C7H7ClO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | YUKILTJWFRTXGB-UHFFFAOYSA-N |
M.W : | 142.58 | Pubchem ID : | 17833 |
Synonyms : |
|
Num. heavy atoms : | 9 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.14 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 37.94 |
TPSA : | 9.23 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.05 cm/s |
Log Po/w (iLOGP) : | 2.19 |
Log Po/w (XLOGP3) : | 2.98 |
Log Po/w (WLOGP) : | 2.35 |
Log Po/w (MLOGP) : | 2.41 |
Log Po/w (SILICOS-IT) : | 2.48 |
Consensus Log Po/w : | 2.48 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.03 |
Solubility : | 0.133 mg/ml ; 0.000936 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.84 |
Solubility : | 0.207 mg/ml ; 0.00145 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.12 |
Solubility : | 0.109 mg/ml ; 0.000766 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.23 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | 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 |
---|---|---|
97% | With N-Bromosuccinimide; iodine In acetonitrile for 12 h; Darkness | General procedure: To a reaction tube charged with NBS (1.5 equiv, 0.3 mmol), catalyst (10 molpercent, 0.02 mmol) and CH3CN (1.0 mL),was added para-chloroanisole 1a (0.2 mmol). After being stirred at room temperature for 12 h in dark, the reaction was quenched by saturated aq. solution of Na2S2O3 (2 mL). The resulting mixture was extracted by ethyl acetate (3 5 mL). The combined organic extracts were washed by brine (10 mL), dried over Na2SO4 and filtered through a pad of Celite. The filtrate was concentrated under reduced pressure and the residuewas purified by flash chromatography on a silica gel column with petroleum ether/dichloromethane (5:1) as the eluent to give 4.3.1. 2-Bromo-4-chloroanisole (2a) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1 -(2-Chloro-4-methoxy-phenyl)-ethanoneTo a mixture of AICI3 (42.08 g; 315.60 mmol) in CH2CI2 (300 ml.) was added dropwise 3-chloroanisole (22.50 g; 157.80 mmol), at -300C. To the resulting mixture was added dropwise a solution of AcCI (10.50 ml 147.63 mmol) in CH2CI2 (100 ml.) at such a rate to keep the temperature below -15C. The resulting mixture was stirred for 4 hours at -100C. Subsequently, the mixture was poured onto ice and extracted with CH2CI2. The combined organic layers, were dried (MgSO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiO2, Et2O/hexanes 1 :9) to afford 1 -(2-chloro-4-methoxy-phenyl)-ethanone (17.68 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With carbon monoxide In N,N-dimethyl-formamide at 150℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium fluoride; monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0) In toluene at 80℃; for 26h; | |
97% | With KF In toluene | 109 3-methoxy-4'-methoxy-1,1'-biphenyl (Table 17, Entry 4) Example 109 3-methoxy-4'-methoxy-1,1'-biphenyl (Table 17, Entry 4) 3-Chloroanisole (76 mg, 0.54 mmol) reacted with 4-methoxyphenylboronic acid (117 mg, 0.77 mmol) using 1 mol % of Pd(dba)2/Ph5FcP(t-Bu)2 and KF (87 mg, 1.50 mmol) in toluene at 80° C. to give the title compound (112 mg, 97%) as a colorless oil: 1H-NMR (300 MHz CDCl3): δ 7.57 (d, 2H, J=8.7 Hz), 7.37 (t, 1H, J=7.8 and 8.1 Hz), 7.17 (m, 2H), 7.01 (d, 2H, J=8.7 Hz), 6.88-6.97 (m, 1H), 3.89 (s, 3H), 3.88 (s, 3H). 13C{1H}-NMR (100 MHz, CDCl3): δ 159.86, 159.17, 142.28, 135.51, 129.66, 128.13, 119.21, 114.09, 112.44, 111.93. GC/MS (EI): m/z 214 (M+), 199, 171, 128. Anal. Calcd for C14H4O2: C, 78.48; H, 6.59. Found C, 78.46: H, 6.62. |
72% | With potassium carbonate at 70℃; | 2.2.1. General procedure for the Suzuki reaction General procedure: In a round-bottom flask containing a mixture of PEG (6 mL) as the solvent, a mixture of aryl halide (1.0 mmol), phenylboronic acid (1.2 mmol), K2CO3 (2.0 mmol), and the synthesized catalyst (3 mol%) were stirred at 70 °°C. The reaction’s progress was assessed by TLC (hexane/ ethyl acetate, 80:20) and GC. After the completion of the reaction, the organic layer was washed with water (3 × 10 mL) and ethyl acetate (3 × 10 mL) and dried over anhydrous MgSO4. The related products were purified using column chromatography (n-hexane/ethyl acetate, 5:1) and characterized by 1 H NMR and 13C NMR analyses and summarized in the supporting information. |
With potassium phosphate; n-butyllithium; [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; potassium iodide 1.) dioxane, room temperature, 10 min, 2.) 80 deg C, 16 h; Yield given. Multistep reaction; | ||
With C17H16Cl2N4O2Pd; sodium hydrogencarbonate In dimethyl sulfoxide at 120℃; for 12h; Schlenk technique; Inert atmosphere; | 11 Example 11 Under the protection of nitrogen, m-chloromethoxybenzene (0.4 mmol) was sequentially added to the dried Schlenk reaction tube. Oxyaryl boronic acid (0.8 mmol), NaHCO3 (0.8 mmol), tricarbene palladium metal complex catalyst (0.04 mmol) and DMSO (2.5mL); the ratio of the amount of m-chloromethoxybenzene to p-methoxyarylboronic acid is 1: 2; m-chloromethoxybenzene and The amount of NaHCO3 is 1: 2; the amount of m-chloromethoxybenzene and triazole carbene palladium metal complex catalyst is Is 1: 0.1. Then, the reaction tube was placed in an oil bath at 120 ° C for reaction, and the progress of the reaction was monitored by thin layer chromatography. After 12 hours, The mixture was cooled to room temperature, diluted with purified water, and extracted with ethyl acetate, and the organic phases were combined. Organic phase The solution was washed with acid solution and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated, and separated by column chromatography. As a stationary phase, the product was purified and separated with a mixed solvent of ethyl acetate and petroleum ether in different proportions as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,1'-bis(di-tertbutylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In tetrahydrofuran at 70℃; for 2h; | |
89% | With C40H44ClN3Pd; sodium t-butanolate In toluene at 80℃; for 3h; Inert atmosphere; | 4.2.3. General procedure for the complex 3a-catalyzed α-arylationof ketones General procedure: Under N2 atmosphere, 3a (1.0 or 2.0 mol%), NaOtBu (2.0 equiv), toluene (1.0 mL), propiophenones 7 (0.5 mmol) and aryl chlorides 4 (0.6 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred vigorously at 80 °C for 3 h. Then the solvent was removed under reduced pressure and the residue was puried by flash column chromatography (SiO2) to give the corresponding products. |
88% | With sodium t-butanolate In tetrahydrofuran at 70℃; for 1h; |
88% | With 2-methoxy-6-(N-methyl-N-phenyl-amino)phenyl(dicyclohexyl)phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 16.5h; Schlenk technique; Inert atmosphere; | 4 Example 4 Synthesis of 2-(3′-Methoxyphenyl)-1-phenyl-1-enthanone This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are m-methoxyphenyl chloride (143.4 mg, 1.0 mmol), propiophenone (160.6 mg, 1.2 mmol), palladium acetate (6.6 mg, 0.029 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyl(dicyclohexyl)phosphine (18.4 mg, 0.045 mmol), t-BuONa (115.0 mg, 1.2 mmol) in 3 mL dry toluene at 110° C. for 16.5 h. 2-(3′-Methoxyphenyl)-1-phenyl-1-enthanone (212.6 mg) was obtained with a yield of 88% as liquid. 1H NMR (300 MHz, CDCl3) δ 8.02-7.96 (m, 2H, ArH), 7.46-7.39 (m, 1H, ArH), 7.38-7.30 (m, 2H, ArH), 7.21 (t, J=8.0 Hz, 1H, ArH), 6.94-6.88 (m, 2H, ArH), 6.77-6.72 (m, 1H, ArH), 4.69 (q, J=6.9 Hz, 1H, CH), 3.71 (s, 3H, OCH3), 1.56 (d, J=6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3) δ 199.8, 159.8, 142.8, 136.2, 132.5, 129.7, 128.5, 128.2, 119.9, 113.3, 111.8, 54.8, 47.6, 19.2; IR (neat) v (cm-1) 3059, 2973, 2932, 2835, 1682, 1598, 1486, 1455, 1372, 1312, 1263, 1215, 1181, 1149, 1045, 1002; MS (70 eV, El) m/z (%): 241 (M++1, 2.10), 240 (M+, 11.90), 105 (100). |
83% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 80℃; for 6h; Inert atmosphere; | |
81% | With sodium t-butanolate In 1,4-dioxane at 60℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With NHC-Pd(II)-Im; potassium tert-butylate; In toluene; for 4h;Inert atmosphere; Reflux; | General procedure: Under N2 atmosphere, KOtBu (114.0 mg, 1.0 mmol), NHC-Pd(II)-Im complex 1 (5.2 mg, 1.0 mol %), dry toluene (1.0 mL), chlorobenzene 2a (0.8 mmol), and aniline 3a (0.96 mmol) were successively added into a Schlenk reaction tube. The reaction mixture was stirred under reflux for 4 h. Then the solvent was removed under reduced pressure and the residue was purified by a flash chromatography on silica gel to give the pure product 4a. |
91% | With Pd(pi-crotyl)(QPhos)Cl; sodium t-butanolate; In toluene; at 80℃; for 3h;Inert atmosphere; | General procedure: A Schlenk flask was charged with the catalyst, NaOt-Buand aryl halide, if solid, and the flask was evacuated and backfilled with nitrogen three times. Subsequently, a solution of the aryl halide, if liquid, and the amine in toluene was added. The resulting reaction mixture was stirred under nitrogen at the indicated temperature and time (see Tables incommunication). The crude mixture was absorbed onto silica gel (Merck Silica Gel 60 (0.040-0.063 mm)) and purified by flash column chromatography (MTBE/40-60 petroleum ether eluent). |
55% | With C28H29Cl2N3OPd; potassium tert-butylate; In toluene; at 110℃; for 15h;Schlenk technique; Inert atmosphere; | General procedure: A Schlenk ask was charged with the required aryl chloride (0.25 mmol), amine (0.30 mmol), N-heterocyclic carbene-palladium(II) complex (2 mol%), KOtBu (1.3 equiv), and toluene (0.5 mL). The mixture was stirred at 110 C for 15 h under N2. After cooling, the mixture was evaporated and the product was isolated by preparative TLC on silica gel plates. The puried products were identied by 1H NMR spectra, and their analytical data are given in the Supporting Information. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With C8H8NO(1-)*C30H45P*C7H7O3S(1-)*Pd(2+); potassium acetate; In tetrahydrofuran; at 20℃;Glovebox; Inert atmosphere; | General procedure: In a glovebox with an N2 atmosphere, to a vial containing bis(pinacolato)diboron (0.6 mmol, 3 equiv.), complex 1 (8.5 mg, 0.01 mmol, 0.05 equiv.), potassium acetate (78.5 mg, 0.8 mmol, 4 equiv.), THF (1 mL), was added aryl chloride (0.2 mmol, 1 equiv.). The mixture was allowed to react at room temperature for 24-48 h. After quenching with water, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with brine and then evaporated under vacuum. Flash chromatography on silica gel Flash chromatography on silica gel (hexane:ethyl acetate = 100:0 to 85:15) yielded the product. |
81% | With (2,2,2-trifluoroethoxy)trimethylsilane; cesium fluoride; dichlorobis(trimethylphosphine)nickel; In tetrahydrofuran; at 100℃; for 12h;Inert atmosphere; Sealed tube; | Under an argon atmosphere,2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel,70.7 mg (0.5 mmol) of 3-chloroanisole,152 mg (1.0 mmol) of cesium fluoride,140 mg (0.55 mmol) of 4,4,5,5,4 ', 4', 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolanyl)180 mg (1.05 mmol) of trimethyl (2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed,And the mixture was stirred at 100 C. for 12 hours.After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous solution of ammonium chloride was added, and the mixture was extracted three times with 8 mL of ethyl acetate, and the obtained organic phases were combined.The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1)94 mg (colorless liquid, yield 81%) of 2- (3-methoxyphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium hexamethyldisilazane; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); zinc dibromide In tetrahydrofuran; toluene at 60℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With [Pd(2-aminobiphenyl)(PCyp2ArXyl2)](OMs); sodium t-butanolate In 1,4-dioxane at 100℃; for 19h; Inert atmosphere; Schlenk technique; | |
95% | With monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 100℃; for 24h; | |
95% | With sodium t-butanolate In toluene | 57 N-n-hexyl-3-methoxyaniline(Table 7, Entries 7 and 8) Example 57 N-n-hexyl-3-methoxyaniline(Table 7, Entries 7 and 8) 3-Chloroanisole (74 mg, 0.52 mmol) reacted with n-hexylamine (65 mg, 0.64 mmol) according to procedure B using 1 mol % of Pd(dba)2, 2 mol % of Ph5FcP(t-Bu)2, and sodium tert-butoxide (58 mg, 0.60 mmol) in toluene at 100° C. to give the title compound (103 mg, 95%) as a colorless oil. |
86% | With (±)-[2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]bis(triphenylphosphite)nickel(0) toluene solvate; sodium t-butanolate In toluene at 80℃; Inert atmosphere; | |
83% | With tris-(dibenzylideneacetone)dipalladium(0); C33H48N7P; sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox; | |
68% | With sodium t-butanolate In toluene at 100℃; for 24h; | |
55% | With sodium t-butanolate In toluene at 80℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With (SC8H4C(CF3)NC6H4OCH3)PdCl(tricyclohexylphosphine)2; caesium carbonate In 1,4-dioxane at 100℃; Inert atmosphere; | |
87% | With potassium phosphate; monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0) In toluene at 80℃; for 23h; | |
87% | With potassium phosphate In toluene | 108 3-methoxy-2'-methyl-1,1'-biphenyl (Table 17, Entry 3) Example 108 3-methoxy-2'-methyl-1,1'-biphenyl (Table 17, Entry 3) 3-3-Chloroanisole (71 mg, 0.50 mmol) reacted with 2-methylphenylboronic acid (82 mg, 0.60 mmol) using 3 mol % of Pd(dba)2/Ph5FcP(t-Bu)2 and K3PO4 (318 mg, 1.50 mmol) in toluene at 80° C. to give the title compound (86 mg, 87%) as a colorless oil: 1H-NMR (400 MHz, CDCl3): δ 7.39 (t, 1H, J=7.6 and 8.0 Hz), 7.33-7.30 (m, 4H), 6.99-6.94 (m, 3H), 3.89 (s, 3H), 2.35 (s, 3H). 13C{1H}-NMR (100 MHz, CDCl3): δ 159.23, 143.32, 141.75, 135.27, 130.25, 129.60, 129.00, 127.26, 125.67, 121.63, 114.78, 112.23, 55.16, 20.42. GC/MS (EI): m/z 198 (M+), 167 (M+-OMe). Anal. Calcd for C14H14O: C, 84.81; H, 7.12. Found C, 84.72; H, 7.09. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 2'-dicyclohexylphosphanyl-6-methoxy-biphenyl-3-sulfonic acid; palladium diacetate; sodium t-butanolate In diethylene glycol dimethyl ether at 120℃; for 72h; Inert atmosphere; | 9 4.8. Methyl-3-methoxyphenylamine (29) NaOtBu (577mg, 6.0mmol) was added to a dry round-bottom flask and the solid stirred for 12h at 120°C under Ar. 42 Diglyme (7 mL) was added and the resulting suspension was sequentially treated with 15 N-methylaniline (306µg, 3.0mmol), 14 3-chloroanisole (365μl, 3.0mmol) and a suspension of 40 Pd(OAc)2 (14mg, 0.06mmol) and ligand 36 4b (28mg, 0.06mmol) in diglyme (2 mL). After being stirred at 120°C for 3 d, the reaction mixture was passed through a bed of silica gel and the residue was washed with MeOH. The filtrate was evaporated to dryness in vacuo to give 638mg (quant.) of compound 29 as a yellow solid, mp. 67°C (MeOH). IR (neat): υ=3058, 3034, 2999, 2938, 2833, 2812, 1591, 1575, 1495, 1456, 1347, 1273, 1214, 1168, 1127, 1094, 1048, 990, 929, 847, 753, 691cm-1. 13C NMR (CDCl3, 400MHz): δ=40.40 (q, 1C), 55.26 (q, 1C), 105.70 (d, 1C), 106.00 (d, 1C), 112.62 (d, 1C), 121.70 (d, 2C), 121.96 (d, 1C), 128.44 (d, 2C), 129.08 (d, 1C), 148.98 (s, 1C), 150.49 (s, 1C), 160.66 (s, 1C). MS (EI+, 70eV): m/z=213 (100) [M+], 197 (5), 154 (5). HRMS (EI+, 70eV): m/z=C14H15NO calcd.213.1154; found 213.1155. |
97% | With sodium t-butanolate In toluene at 80℃; for 1h; | |
96% | With potassium <i>tert</i>-butylate; C36H43Cl2N3OPd In toluene at 130℃; for 12h; Inert atmosphere; Schlenk technique; | 4.3. General procedure for the complex 2a-catalyzed Buchwald-Hartwig amination of aryl chlorides General procedure: Under N 2 atmosphere, KO t Bu (102.1 mg, 1.3 equiv) and a so- lution of complex 2a (10-50 μL, 0.01-0.05 mol%, prepared from 5.0 mg of complex 2a in 1.0 mL dichloromethane) were added into a Schlenk reaction tube. The tube was sealed and the sol- vent was removed under reduced pressure. Then toluene (1.0 mL), amines (0.84 mmol) and aryl chlorides (0.70 mmol) were succes- sively added. The mixture was stirred vigorously at the specified temperature for 6-24 h. Then the solvent was removed under reduced pressure and the residue was purified by flash column chro- matography on silica gel to give the corresponding products. |
95% | With tris(dibenzylideneacetone)dipalladium (0); sodium t-butanolate; 2,8,9-tris(2-methylpropyl)-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane In toluene Heating; | |
94% | With tris-(dibenzylideneacetone)dipalladium(0); keYPhos; potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Glovebox; Inert atmosphere; | |
93% | With C36H45Cl2N3OPd; potassium <i>tert</i>-butylate In 1,4-dioxane at 90℃; for 1h; Inert atmosphere; Schlenk technique; | |
93% | With C33H40ClN3O2Pd; potassium <i>tert</i>-butylate In toluene at 90℃; for 6h; Inert atmosphere; Schlenk technique; Sealed tube; | 4.2.2. General procedure for the complex 3a-catalyzed Buchwald-Hartwig amination of aryl chlorides General procedure: Under a N2 atmosphere, KOtBu (102.1 mg, 1.3 equiv) and a so-lution of complex 3a (10e50 mL, 0.01e0.05 mol%, prepared from4.6 mg of complex 3a in 1.0 mL dichloromethane) were added into aSchlenk reaction tube. The tube was sealed and the solvent wasremoved under reduced pressure. Then toluene (0.5 mL), amines(0.84 mmol) and aryl chlorides (0.70 mmol) were successivelyadded. The mixture was stirred vigorously at the specied tem-perature for 3e24 h. Then the solvent was removed under reducedpressure and the residue was puried by ash column chroma-tography (SiO2) to give the corresponding products. |
91% | With Pd((CH3)2C6H3NC(CH3)CHC(CH3)NC6H3(CH3)2)(CH3)(P(CH2CH3)3); potassium <i>tert</i>-butylate In 1,2-dimethoxyethane at 20℃; for 8h; | |
88% | With tris-(dibenzylideneacetone)dipalladium(0); C33H48N7P; sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox; | |
86% | With sodium t-butanolate In toluene at 100℃; for 20h; | |
85% | With C36H43Cl2N3Pd; potassium <i>tert</i>-butylate In 1,4-dioxane at 130℃; for 18h; Inert atmosphere; Schlenk technique; | |
73% | With C24H39O2P*H(1+)*BF4(2+); palladium diacetate; potassium hydroxide In toluene at 110℃; for 24h; Inert atmosphere; Schlenk technique; | |
73% | With [Pd(2-aminobiphenyl)(PiPr2ArXyl2)](OMs); sodium t-butanolate In tetrahydrofuran at 80℃; for 19h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetraethylammonium bromide In methanol Electrolysis; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); 2,8,9-tris(2-methylpropyl)-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane; In toluene; at 100℃; for 24h;Product distribution / selectivity; | General Procedure for the Coupling of Aryl Halides with Aza-crown ethers using the Pd2(dba)3/1 or Pd2(dba)3/2 catalyst system (Tables 1 and 2): An oven-dried Schlenk flask equipped with a magnetic stirring bar was charged with Pd2(dba)3 (0.5-2 mol %, see Tables 1 and 2), an appropriate aza-crown ether (1.2 mmol), and NaO-t-Bu (1.4 mmol) or Cs2CO3 (1.5 mmol) inside a glovebox. If the aryl halide (1.0 mmol) was a solid, it was also added at this time. The flask was capped with a rubber septum and removed from the glove box. Ligand 1 or 2 (2-8 mol %) was then added via syringe from a stock solution (2 mM in toluene). Aryl halide (if a liquid, 1.0 mmol) and toluene (3 mL) were then successively added via syringe. The reaction mixture was heated at the temperature indicated (see Tables 1 and 2) for 24 hours. The mixture was then cooled to room temperature, adsorbed onto silica gel and then purified by column chromatography using initially 10% ethyl acetate/hexanes and then ethyl acetate as eluents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium t-butanolate In 1,2-dimethoxyethane at 100℃; for 24h; | |
97% | With C50H72ClPPd; 2,6-bis(2,4,6-triisopropylphenyl)phenyldicyclohexylphosphine; caesium carbonate In <i>tert</i>-butyl alcohol at 100℃; for 6h; | |
80% | With [Pd(2-aminobiphenyl)(PiPr2ArXyl2)](OMs); sodium t-butanolate In tetrahydrofuran at 80℃; for 19h; Inert atmosphere; Schlenk technique; |
77% | With sodium t-butanolate In toluene at 100℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With [Pd(2-aminobiphenyl)(PCyp2ArXyl2)](OMs); sodium t-butanolate In tetrahydrofuran at 100℃; for 19h; Inert atmosphere; Schlenk technique; | |
98% | With (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-t-butylphosphine; sodium t-butanolate In 1,2-dimethoxyethane at 80℃; for 48h; | |
98% | With sodium t-butanolate In 1,2-dimethoxyethane at 80℃; for 48h; |
97% | With potassium phosphate; copper(l) iodide; N<SUP>1</SUP>,N<SUP>2</SUP>-bis(2,4,6-trimethoxyphenyl)oxalamide In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | A solution of 3-chloroanisole (1.753 g, 12.3 mmol) in THF (60 mL) was cooled to - 95 C. A solution of sec-BuLi in cyclohexane (1.3M, 9.5 mL, 12.4 mmol) was added dropwise keeping the internal temperature BELOW-90 C. After 1H a solution of IA (3.15 g, 12.4 mmol) in THF (5 mL) was added dropwise. The mixture was allowed to reach room temperature overnight. Diethylether (100 mL) was added. The organic layer was washed with 1M aqueous NA2S03, H20, brine and dried over NA2S04. The crude product was adsorbed onto silica gel. After purification by flash chromatography using silica gel, eluting with heptanes/EtOAc, 98: 2, the product was obtained as colorless crystals Yield: 2.19g, 66%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N-Bromosuccinimide; iodine; In acetonitrile; for 12h;Darkness; | General procedure: To a reaction tube charged with NBS (1.5 equiv, 0.3 mmol), catalyst (10 mol%, 0.02 mmol) and CH3CN (1.0 mL),was added para-chloroanisole 1a (0.2 mmol). After being stirred at room temperature for 12 h in dark, the reaction was quenched by saturated aq. solution of Na2S2O3 (2 mL). The resulting mixture was extracted by ethyl acetate (3 5 mL). The combined organic extracts were washed by brine (10 mL), dried over Na2SO4 and filtered through a pad of Celite. The filtrate was concentrated under reduced pressure and the residuewas purified by flash chromatography on a silica gel column with petroleum ether/dichloromethane (5:1) as the eluent to give 4.3.1. 2-Bromo-4-chloroanisole (2a) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonium hydroxide; potassium phosphate; In dodecane; water; ethyl acetate; | Example 199 3-Methoxy-N-hexylaniline from 3-chloroanisole CuOAc (6 mg, 0.05 mmol), <strong>[19311-91-2]N,N-diethylsalicylamide</strong> (39 mg, 0.20 mmol) and K3PO4 (425 mg, 2.0 mmol) were put into a screw-capped test tube with a Teflon-lined septum. The tube was then evacuated and backfilled with argon (3 cycles). 3-Chloroanisole (122 muL, 1.0 mmol) and n-hexylamine (0.5 mL, as solvent) were added by syringes. The reaction mixture was stirred at 130 C. for 24 h. The reaction mixture was allowed to reach room temperature. Ethyl acetate (~2 mL), water (~10 mL), ammonium hydroxide (~0.5 mL) and dodecane (227 muL) were added. The organic phase was analyzed by GC which afforded 64% conversion of 3-chloroanisole and 40% GC yield of the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 4 A molecular sieve; sodium phenoxide In dimethyl sulfoxide at 100℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With 4 A molecular sieve; sodium phenoxide In dimethyl sulfoxide at 120℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 4 A molecular sieve; sodium phenoxide In dimethyl sulfoxide at 120℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With 4 A molecular sieve; sodium phenoxide In dimethyl sulfoxide at 120℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: tert-butyl propionate With sodium hexamethyldisilazane In toluene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: 1-chloro-3-methoxy-benzene With di-μ-bromobis(tri-tert-butylphosphino)dipalladium(I) In toluene at 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: potassiumhexacyanoferrate(II) trihydrate; 1-chloro-3-methoxy-benzene With sodium 2'‐(dicyclohexylphosphaneyl)‐2,6‐diisopropyl‐[1,1'‐biphenyl]‐4‐sulfonate; palladium diacetate; potassium carbonate In water at 120℃; for 12h; Inert atmosphere; Sealed tube; Stage #2: potassiumhexacyanoferrate(II) trihydrate; 1-chloro-3-methoxy-benzene With potassium carbonate In water at 120℃; for 12h; Inert atmosphere; Sealed tube; | 2.3 General Procedure forPalladium-CatalyzedCyanation ofAryl ChlorideswithK4[Fe(CN)6]·3H2O inPEG-400/H2O General procedure: A pressure tube equipped with a magnetic stir bar wascharged with Pd(OAc)2 (4.5mg, 0.02mmol), XPhos-SO3Na(20.9 mg, 0.04 mmol), K4[Fe(CN)6]·3H2O (105.6 mg,0.25mmol), K2CO3(35mg, 0.25mmol) and PEG-400(1.0mL). The reaction tube was evacuated and backfilledwith argon (this sequence was carried out three times) andthen aryl chloride (1.0mmol, if liquid) and water (1.0mL)were added by syringe (aryl chlorides that were solids atroom temperature were added with the palladium catalystand ligand). The reaction tube was sealed and the reactionmixture was stirred for 12h at the indicated temperature.After being cooled to room temperature, the mixture wasextracted with cyclohexane (3 × 10mL). The combinedcyclohexane phase was concentrated under reduced pressure,and the residue was purified by flash column chromatographyon silica gel (light petroleum ether-ethyl acetate)to afford the desired aryl nitrile 2.The residue of the extraction was heated to 50C invacuo for 30min to remove the residual cyclohexane, andthen subjected to a second cycle of the cyanation reactionby charging with the same substrates (aryl chloride,K4[Fe(CN)6]·3H2O and K2CO3)under the same conditionswithout further addition of Pd(OAc)2 and Xphos-SO3Na. |
85% | With di-tert-butyl{2′-isopropoxy-[1,1′-binaphthalen]-2-yl}phosphane; palladium diacetate; potassium carbonate; phenylboronic acid In water; <i>tert</i>-butyl alcohol at 100℃; for 6h; Inert atmosphere; Schlenk technique; | general procedures for the cyanation of aryl chlorides and mesylates General procedure: An oven-dried Schlenk tube was evacuated and backfilled with nitrogen. The Schlenk tube was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol ), L1 (36.5 mg, 0.08 mmol), PhB(OH)2 (6.1 mg, 0.05 mmol), and t-BuOH (2 mL), and the mixture was stirred for half hour at 50 °C. After cooling to r.t., aryl chloride or mesylates (1.00 mmol), K4[Fe(CN)6]·3H2O (211.2 mg, 0.50 mmol), K2CO3 (138.2 mg, 1.00 mmol), and H2O (2 mL) were added. The septum was replaced with an inside reflux condenser, and then the Schlenk tube was placed in an oil bath preheated to 100 °C (120 °C for aryl mesylates) with stirring for 6 h (24 h for aryl mesylates). Then the reaction mixture was allowed to cool to r.t., extracted with CH2Cl2, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel. |
97 %Chromat. | With palladium diacetate; potassium carbonate; XPhos In 1,4-dioxane; water at 120℃; for 10h; sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C35H44Cl2N4Pd; potassium <i>tert</i>-butylate In tetrahydrofuran at 130℃; for 12h; Inert atmosphere; Sealed tube; | |
97% | With C40H44ClN3Pd; potassium <i>tert</i>-butylate In toluene at 110℃; for 24h; Inert atmosphere; | 4.2.2 General procedure for the complex 3a-catalyzed amination of aryl chlorides General procedure: Under N2 atmosphere, KOtBu (1.3 equiv), toluene (1.0 mL), amines 5 (0.84 mmol), aryl chlorides 4 (0.7 mmol) and finally a solution of complex 3a (20-100μL, 0.01-0.05 mol%, prepared from 0.014 mmol 3a in 4.0mL toluene) were successively added into a Schlenk reaction tube. The mixture was stirred vigorously at 110 °C for 24h. Then the solvent was removed under reduced pressure and the residue was purified by flash column chromatography (SiO2) to give the corresponding products. |
93% | With C36H43Cl2N3Pd; potassium <i>tert</i>-butylate In 1,4-dioxane at 130℃; for 18h; Inert atmosphere; Schlenk technique; |
92% | With C33H40ClN3O2Pd; potassium <i>tert</i>-butylate In toluene at 90℃; for 6h; Inert atmosphere; Schlenk technique; Sealed tube; | 4.2.2. General procedure for the complex 3a-catalyzed Buchwald-Hartwig amination of aryl chlorides General procedure: Under a N2 atmosphere, KOtBu (102.1 mg, 1.3 equiv) and a so-lution of complex 3a (10e50 mL, 0.01e0.05 mol%, prepared from4.6 mg of complex 3a in 1.0 mL dichloromethane) were added into aSchlenk reaction tube. The tube was sealed and the solvent wasremoved under reduced pressure. Then toluene (0.5 mL), amines(0.84 mmol) and aryl chlorides (0.70 mmol) were successivelyadded. The mixture was stirred vigorously at the specied tem-perature for 3e24 h. Then the solvent was removed under reducedpressure and the residue was puried by ash column chroma-tography (SiO2) to give the corresponding products. |
92% | With potassium <i>tert</i>-butylate; C36H43Cl2N3OPd In toluene at 130℃; for 12h; Inert atmosphere; Schlenk technique; | 4.3. General procedure for the complex 2a-catalyzed Buchwald-Hartwig amination of aryl chlorides General procedure: Under N 2 atmosphere, KO t Bu (102.1 mg, 1.3 equiv) and a so- lution of complex 2a (10-50 μL, 0.01-0.05 mol%, prepared from 5.0 mg of complex 2a in 1.0 mL dichloromethane) were added into a Schlenk reaction tube. The tube was sealed and the sol- vent was removed under reduced pressure. Then toluene (1.0 mL), amines (0.84 mmol) and aryl chlorides (0.70 mmol) were succes- sively added. The mixture was stirred vigorously at the specified temperature for 6-24 h. Then the solvent was removed under reduced pressure and the residue was purified by flash column chro- matography on silica gel to give the corresponding products. |
88% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium <i>tert</i>-butylate In 1,4-dioxane at 70℃; for 3h; Inert atmosphere; | 4.3. General procedure for the NHC-Pd(II)-Im catalyzed amination reactions of morpholine with aryl chlorides General procedure: Under N2 atmosphere, KOtBu (1.0 mmol), NHC-Pd(II)-Im 2a (1.0 mol %), dry dioxane (1.0 mL), morpholine 3 (0.8 mmol), and aryl chloride 4 (0.7 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred at 70 °C for 3 h. The solvent was removed under reduced pressure and the residue was purified by a flash chromatograph on silica gel to give the pure products 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dmap; bis(η3-allyl-μ-chloropalladium(II)); ruphos; In 1,3,5-trimethyl-benzene; at 140℃; for 20h;Inert atmosphere; | General procedure: after standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Schlenk tube equipped with a magnetic stirring bar was charged with Pd source (see Table 1, Table 2, Table 3 and Table 4), ligand (see Table 1, Table 2, Table 3 and Table 4), N,N-dimethylpyridin-4-amine (DMAP, see Table 1, Table 2, Table 3 and Table 4), and ethyl potassium malonate (see Table 1, Table 2, Table 3 and Table 4). The tube was evacuated and backfilled with argon (this procedure was repeated three times). Under a counter flow of argon, aryl halide (see Table 1, Table 2, Table 3 and Table 4) and solvent (see Table 1, Table 2, Table 3 and Table 4) were added by syringe. The tube was sealed and stirred at room temperature for 10 min. Then the tube was connected to the Schlenk line, which was full of argon, stirred in a preheated oil bath (140-150 C) for the appointed time (20-25 h). Upon completion of the reaction, the mixture was cooled to room temperature and diluted with diethyl ether, and the yields were determined by gas chromatography using 1,3-dimethoxybenzene as the internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: To a flame dried 100mL flask were added 1,3-disustituted benzene (3.0mmol), TMEDA (1.1equiv, 3.3mmol), DIPA (5%equiv, 0.16mmol), and THF (10.0mL). The solution was cooled to -78C for 10min and then n-BuLi (1.1equiv, 3.3mmol) was added dropwise. The mixture was kept at this temperature for 1h; DMF (1.5equiv, 4.5mmol) was added and the mixture was further stirred for another half an hour at -78C. The mixture was allowed to warm up to room temperature and quenched by the addition of saturated NH4Cl-H2O solution (5mL); extracted three times with ethyl acetate (10mL×3). The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The regioselectivity of the crude product was ascertained by 19F NMR (for fluorinated products) or by GC/MS (for nonfluorinated ones) and then subjected to flash chromatography to obtain the desired products which were characterized by 1H NMR, 19F NMR, and 13C NMR spectral data and GC-MS analyses. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | Stage #1: 1-chloro-3-methoxy-benzene With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; bis(pinacol)diborane; 4,4'-di-tert-butyl-2,2'-bipyridine In tert-butyl methyl ether at 80℃; for 1h; Inert atmosphere; Glovebox; Microwave irradiation; Stage #2: 3-trifluoromethyl-thiophenol With pyridine; copper diacetate In N,N-dimethyl-formamide at 135℃; for 1.5h; Inert atmosphere; Microwave irradiation; regioselective reaction; | General procedure: A flask equipped with a magnetic stirrer bar was charged with [Ir(OCH3)(C8H12)]2 (99.0 mg, 0.015mmol), 4,4′-di-tert-butyl-2,2′-dipyridyl (82.0 mg, 0.03 mmol) and pin2B2 (254 mg, 1.0 mmol) in anitrogen-filled glove box. This flask was then covered with a rubber septum and removed from theglove box. Under a nitrogen atmosphere, arene (1.0 mmol) and MTBE (2.0 mL) were added viasyringe, and the reaction vessel was placed under microwave irradiation at 80 °C. After stirring at thistemperature for 1 h, the heterogeneous mixture was cooled to room temperature, after removed thevolatile components under vacuum. The flask was returned to the glove box, Cu(OAc)2 (136 mg, 0.75mmol) was added, the flask was then covered with a rubber septum and removed from the glove box.Under an argon atmosphere, aryl thiol (0.5 mmol), pyridine (0.123 mL, 1.5 mmol) and DMF (2.0 mL)were added via syringe, and the reaction vessel was placed under microwave irradiation at 135 °C.After stirring at this temperature for 1.5 h, the heterogeneous mixture was cooled to room temperatureand diluted with ethyl acetate (20 mL). The resulting solution was directly filtered through a pad ofsilica gel then washed with ethyl acetate (20 mL) and concentrated to give the crude material whichwas then purified by column chromatography (SiO2, hexane) to yield 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With (2,2′-bis(biphenylphosphino)-1,1′-binaphthalene)Ni(η2-NC-Ph); sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium <i>tert</i>-butylate In toluene at 80℃; for 3h; Inert atmosphere; Schlenk technique; | 2.2. General procedure for the NHC-Pd(II)-Im complex 1 catalyzed aarylation General procedure: 1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) weresuccessively added into a Schlenk reaction tube. The mixture wasstirred at the specified temperature for the listed time shown inTables 1-3. The reaction mixture was cooled to room temperature,then the solvent was evaporated under reduced pressure and theresidue was purified by flash column chromatography to give thepure products. |
90% | With NHC-Pd(II)-Im; potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 80℃; for 3h; Inert atmosphere; Schlenk technique; | General procedure for the NHC-Pd(II)-Im complex 1 catalyzed α-arylation Under N2 atmosphere, NHC-Pd(II)-Im complex 1 (6.5 mg, 1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones 3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred at the specified temperature for the listed time shown in Tables 1-3. The reaction mixture was cooled to room temperature, then the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography to give the pure products. |
90% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium <i>tert</i>-butylate In toluene at 80℃; for 3h; Inert atmosphere; Schlenk technique; | 2.2. General procedure for the NHC-Pd(II)-Im complex 1 catalyzed α-arylation General procedure: Under N2 atmosphere, NHC-Pd(II)-Im complex 1 (6.5 mg,1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones 3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred at the specified temperature for the listed time shown inTables 1-3. The reaction mixture was cooled to room temperature,then the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography to give the pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium tert-butylate; In toluene; at 80℃; for 3h;Inert atmosphere; Schlenk technique; | General procedure: 1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) weresuccessively added into a Schlenk reaction tube. The mixture wasstirred at the specified temperature for the listed time shown inTables 1-3. The reaction mixture was cooled to room temperature,then the solvent was evaporated under reduced pressure and theresidue was purified by flash column chromatography to give thepure products. |
80% | With NHC-Pd(II)-Im; potassium tert-butylate; In N,N-dimethyl-formamide; at 80℃; for 3h;Inert atmosphere; Schlenk technique; | Under N2 atmosphere, NHC-Pd(II)-Im complex 1 (6.5 mg, 1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones 3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred at the specified temperature for the listed time shown in Tables 1-3. The reaction mixture was cooled to room temperature, then the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography to give the pure products. |
80% | With PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2); potassium tert-butylate; In toluene; at 80℃; for 3h;Inert atmosphere; Schlenk technique; | General procedure: Under N2 atmosphere, NHC-Pd(II)-Im complex 1 (6.5 mg,1.0 mol%), KOtBu (224.4 mg, 2.0 mmol), toluene (1.0 mL), ketones 3 (2.0 mmol or 0.7 mmol), and aryl chlorides 2 (1.0 mmol) were successively added into a Schlenk reaction tube. The mixture was stirred at the specified temperature for the listed time shown inTables 1-3. The reaction mixture was cooled to room temperature,then the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography to give the pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium phosphate tribasic hydrate; NiIICl(1-naphthyl)(tricyclohexylphosphine)2; tricyclohexylphosphine; In tetrahydrofuran; at 23℃; for 1h;Inert atmosphere; Glovebox; Sealed tube; | General procedure: Cross-Coupling of ortho-, meta-, and para-Substituted, Electron-Rich and Electron-Deficient Aryl Halides and Aryl Mesylates with Aryl Neopentylglycolboronates Catalyzed by NiIICl(1-naph-thyl)(PCy3)2/PCy3 in Anhydrous THF at 23 C; General Procedure 2In an oven-dried test tube charged with a Teflon coated stirring barwere added aryl halide or aryl mesylate (0.3 mmol), aryl neopentyl-glycolboronates (0.315 mmol), K3PO4(H2O)3.2 (191.00 ± 1.00 mg, 0.9mmol), and NiIICl(1-naphthyl)(PCy3)2 (11.73 ± 0.0510 mg, 0.015mmol, 5% catalyst loading). The test tube was brought into a N2 filledglove box (moisture level <2 ppm) through three degassing cycles andPCy3 (8.4 mg, 0.03 mmol, 10% loading) ligand was added. Distilled sol-vent (1 mL) was added inside the glove box and the test tube wassealed by a rubber septum and left stirring at 23 C. A sample was tak-en by syringe and transferred outside the glove box. The sample wasdiluted by distilled THF (0.2 mL) and filtered through a short columnof Al2O3. The filtrate was concentrated and the GC analysis was car-ried out. The reaction mixture was diluted with CH2Cl2 (2 mL), filteredthrough a layer of Al2O3, and washed with CH2Cl2 (3 1 mL). The fil-trate was collected and concentrated under vacuum. The crude prod-uct was purified by column chromatography on silica gel with EtO-Ac/hexane mixture as eluent. The reductive elimination side-productwas also isolated and characterized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With potassium phosphate tribasic hydrate; NiIICl(1-naphthyl)(tricyclohexylphosphine)2; tricyclohexylphosphine; In tetrahydrofuran; at 23℃; for 2h;Inert atmosphere; Glovebox; Sealed tube; | General procedure: Cross-Coupling of ortho-, meta-, and para-Substituted, Electron-Rich and Electron-Deficient Aryl Halides and Aryl Mesylates with Aryl Neopentylglycolboronates Catalyzed by NiIICl(1-naph-thyl)(PCy3)2/PCy3 in Anhydrous THF at 23 C; General Procedure 2In an oven-dried test tube charged with a Teflon coated stirring barwere added aryl halide or aryl mesylate (0.3 mmol), aryl neopentyl-glycolboronates (0.315 mmol), K3PO4(H2O)3.2 (191.00 ± 1.00 mg, 0.9mmol), and NiIICl(1-naphthyl)(PCy3)2 (11.73 ± 0.0510 mg, 0.015mmol, 5% catalyst loading). The test tube was brought into a N2 filledglove box (moisture level <2 ppm) through three degassing cycles andPCy3 (8.4 mg, 0.03 mmol, 10% loading) ligand was added. Distilled sol-vent (1 mL) was added inside the glove box and the test tube wassealed by a rubber septum and left stirring at 23 C. A sample was tak-en by syringe and transferred outside the glove box. The sample wasdiluted by distilled THF (0.2 mL) and filtered through a short columnof Al2O3. The filtrate was concentrated and the GC analysis was car-ried out. The reaction mixture was diluted with CH2Cl2 (2 mL), filteredthrough a layer of Al2O3, and washed with CH2Cl2 (3 1 mL). The fil-trate was collected and concentrated under vacuum. The crude prod-uct was purified by column chromatography on silica gel with EtO-Ac/hexane mixture as eluent. The reductive elimination side-productwas also isolated and characterized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium phosphate tribasic hydrate; Ni<SUP>II</SUP>Cl(1-naphthyl)(tricyclohexylphosphine)<SUB>2</SUB>; tricyclohexylphosphine In tetrahydrofuran at 23℃; for 2h; Inert atmosphere; Glovebox; Sealed tube; | Cross-Coupling of ortho-, meta-, and para-Substituted, Electron-Rich and Electron-Deficient Aryl Halides and Aryl Mesylates with Aryl Neopentylglycolboronates Catalyzed by NiIICl(1-naph-thyl)(PCy3)2/PCy3 in Anhydrous THF at 23 °C; General Procedure 2 General procedure: Cross-Coupling of ortho-, meta-, and para-Substituted, Electron-Rich and Electron-Deficient Aryl Halides and Aryl Mesylates with Aryl Neopentylglycolboronates Catalyzed by NiIICl(1-naph-thyl)(PCy3)2/PCy3 in Anhydrous THF at 23 °C; General Procedure 2In an oven-dried test tube charged with a Teflon coated stirring barwere added aryl halide or aryl mesylate (0.3 mmol), aryl neopentyl-glycolboronates (0.315 mmol), K3PO4(H2O)3.2 (191.00 ± 1.00 mg, 0.9mmol), and NiIICl(1-naphthyl)(PCy3)2 (11.73 ± 0.0510 mg, 0.015mmol, 5% catalyst loading). The test tube was brought into a N2 filledglove box (moisture level <2 ppm) through three degassing cycles andPCy3 (8.4 mg, 0.03 mmol, 10% loading) ligand was added. Distilled sol-vent (1 mL) was added inside the glove box and the test tube wassealed by a rubber septum and left stirring at 23 °C. A sample was tak-en by syringe and transferred outside the glove box. The sample wasdiluted by distilled THF (0.2 mL) and filtered through a short columnof Al2O3. The filtrate was concentrated and the GC analysis was car-ried out. The reaction mixture was diluted with CH2Cl2 (2 mL), filteredthrough a layer of Al2O3, and washed with CH2Cl2 (3 1 mL). The fil-trate was collected and concentrated under vacuum. The crude prod-uct was purified by column chromatography on silica gel with EtO-Ac/hexane mixture as eluent. The reductive elimination side-productwas also isolated and characterized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With NHC-Pd(II)-Im; sodium t-butanolate In tetrahydrofuran at 120℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 49 %Chromat. 2: 12 %Chromat. | In cyclohexane for 0.5h; UV-irradiation; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1,1'-bis-(diphenylphosphino)ferrocene; 5 mol% Pd/C; sodium fluoride In 1,4-dioxane at 150℃; Inert atmosphere; |
Tags: 2845-89-8 synthesis path| 2845-89-8 SDS| 2845-89-8 COA| 2845-89-8 purity| 2845-89-8 application| 2845-89-8 NMR| 2845-89-8 COA| 2845-89-8 structure
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P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
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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