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CAS No. : | 100379-00-8 | MDL No. : | MFCD01009693 |
Formula : | C8H11BO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZXDTWWZIHJEZOG-UHFFFAOYSA-N |
M.W : | 149.98 | Pubchem ID : | 583322 |
Synonyms : |
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.25 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 2.0 |
Molar Refractivity : | 46.2 |
TPSA : | 40.46 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.11 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | 1.56 |
Log Po/w (WLOGP) : | -0.02 |
Log Po/w (MLOGP) : | 0.94 |
Log Po/w (SILICOS-IT) : | 0.15 |
Consensus Log Po/w : | 0.53 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.09 |
Solubility : | 1.22 mg/ml ; 0.00812 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.02 |
Solubility : | 1.43 mg/ml ; 0.00956 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.04 |
Solubility : | 1.36 mg/ml ; 0.00904 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.38 |
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 |
---|---|---|
78% | With iodine; potassium carbonate In acetonitrile at 80℃; for 12 h; Inert atmosphere; Schlenk technique; Sealed tube | General procedure: Arylboronic acid 1 (0.5 mmol) and K2CO3 (1 mmol, 138.0mg) were added to a 20 mL Schlenk-tube equipped with amagnetic stir bar. The tube was evacuated twice and backfilledwith N2. MeCN (2 mL) and I2 (0.75 mmol, 191 mg)were added to the tube at r.t. under a stream of N2, and thetube was sealed and placed into a pre-heated oil bath at 80 °Cfor 8–12 h. The resulting solution was cooled to r.t. and H2O(10 mL) was added. The aq layer was extracted with EtOAc (3 × 5 mL). For products 2s and 2t, HCl (1 M) was added tothe aq solution until pH 2 before extraction. The combinedorganic phase was dried over anhydrous Na2SO4, filteredand concentrated by rotary evaporation. Purification of theresidue by column chromatography on silica gel providedthe desired product 2a–v |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | at 25℃; for 0.333333 h; | General procedure: In a flask containing the appropriate potassiumorganotrifluoroborate (0.5 mmol) in distilled water(1 mL) was added montmorillonite K10 (150percent m/m). Themixture was stirred for the time indicated in Scheme 1at room temperature. After this period, the mixture wasextracted with EtOAc (3 × 10 mL) and the organic phasewas washed with water (2 × 15 mL). The organic phasewas dried over anhydrous MgSO4, filtered and the solventwas removed in vacuo to yield the corresponding boronicacids 2a-o. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With C58H82Cl4N6Pd2; potassium <i>tert</i>-butylate In water; isopropyl alcohol at 80℃; for 4h; Schlenk technique; Inert atmosphere; | General procedure for the Suzuki-Miyaura reaction General procedure: A Schlenk flask was charged with the required aryl chloride (0.50 mmol), arylboronic acid (0.75 mmol), dinuclear NHC-palladium(II) complex (1.0 mol%), KOtBu (2.0equiv), iPrOH (0.4 mL) and H2O (0.8 mL). The mixture was stirred at 80 °C for 4 h under N2. After cooling, the reaction mixture was evaporated, and the product was isolated by preparative TLC on silica gel plates. |
74% | With potassium <i>tert</i>-butylate; C61H90Cl4N6Pd2 In ethanol at 27℃; for 24h; Sealed tube; | |
72% | With imidazolium salt C17H25N2O2(1+)*CF3SO3(1-); potassium <i>tert</i>-butylate; potassium hydride In tetrahydrofuran; water at 20℃; for 24h; |
57% | With potassium phosphate; C114H132Cl6N10Pd3 In water; isopropyl alcohol at 80℃; for 6h; Inert atmosphere; Schlenk technique; | |
With (η3-allyl)chloro(7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolidinylidene)palladium(II); potassium <i>tert</i>-butylate In 1,4-dioxane at 80℃; for 1h; Inert atmosphere; | ||
> 99 %Chromat. | With (IPr)Pd(1-t-Bu-indenyl)Cl; potassium carbonate In tetrahydrofuran; methanol at 20℃; for 1h; Inert atmosphere; | |
16 %Chromat. | With potassium phosphate; chlorido[3-(2-(piperidinyl)pyrimidin-4-yl-5-ido)-1-mesityl-1H-imidazolylidene](pyridine)palladium(II) In water; isopropyl alcohol at 90℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With trans-dichloro(1,3-bis-(2,6-diisopentylphenyl)imidazolylidinium)(3-chloro-pyridine); potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol at 65℃; Inert atmosphere; Molecular sieve; | |
87% | With potassium phosphate In tetrahydrofuran; toluene at 110℃; for 16h; | |
78% | With chloro[(1,2,3-n)-3-phenyl-2-propenyl][1,3-bis(2,7-dicyclooctylnaphthalen-1-yl)-imidazolin-2-ylidene] palladium(II); potassium <i>tert</i>-butylate In toluene at 20℃; for 20h; Inert atmosphere; |
48% | With tris-(dibenzylideneacetone)dipalladium(0); 1-methyl-2-(naphthalen-1-yl)-3-(diphenylphosphino)-1H-indole; caesium carbonate In 1,4-dioxane at 110℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 20h; | 3-Bromobenzaldehyde (18.5 g, 100 mmol) and 2,6-dimethylphenylboronic acid (21.0 g, 140 mmol) were dissolved in a mixture of 1 M aqueous sodium carbonate solution (200 mL), ethanol (100 mL) and toluene (200 mL). The air was substituted with argon gas, and tetrakis(triphenylphosphine)palladium(0) (5.78 g, 5.00 mmol) was added. The reaction mixture was stirred under an argon atmosphere at 80C for 20 hr. After cooling the reaction mixture, water was added and the mixture was diluted with ethyl acetate. The insoluble material was filtered off through celite. The organic layer in the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-10% ethyl acetate/hexane) to give the title compound (20.4 g, yield 97%) as a colorless oil. MS m/z 211 (MH+). |
96% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 80℃;Inert atmosphere; | 3-Bromobenzaldehyde (1.8 g, 10 mmol) and (2,6-dimethylphenyl)boronic acid (2.1 g, 14 mmol) were dissolved in a mixture of 1 M aqueous sodium carbonate solution (20 mL), EtOH (10 mL), and toluene (20 mL). After argon substitution, tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. The reaction mixture was stirred under argon atmosphere at 80 C for 20 h. The reaction mixture was cooled, and water was added to the reaction mixture. The mixture was diluted with AcOEt, and the insoluble material was filtered through Celite. The organic layer of the filtrate was washed with brine, dried over anhydrous magnesium sulfate, and concentrated. The crude residue was purified by silica gel chromatograph using a mixture of petroleum ether/ethyl acetate (20 : 1, v/v) as eluent to afford the product 7a (2.1 g, 96%) as a colorless oil. 1H NMR (300 MHz, DMSO-d6) δ: 10.06 (s, 1H), 7.86-7.90 (m, 1H), 7.67-7.69 (m, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.42-7.46 (m, 1H), 7.11-7.23 (m, 3H), 2.02 (s, 6H). |
83% | With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In ethanol; toluene; at 80℃; for 22h;Inert atmosphere; | 3-bromo-benzaldehyde (370.4 mg, 2.002 mmol), 2,6- dimethyl phenyl boronic acid (420.5 mg, 2.804 mmol), saturated aqueous sodium hydrogen carbonate solution (1M solution, 4 mL, 4.001 mmol) ethanol (2.2 mL) of and in a mixed solution of toluene (4 mL), tetrakis (triphenylphosphine) palladium (0) (114.9 mg, 0.099 mmol) was added, under an argon atmosphere and stirred for 22 hours at 80 C.. The reaction mixture was cooled, water (5 mL) and ethyl acetate (10 mL) was added and filtered over Celite (registered trademark). Was separated into aqueous and organic layers, the aqueous layer was extracted twice with ethyl acetate (20 mL), the combined organic layers were extracted with brine (30 mL), further sedge aqueous layer of ethyl acetate (20 and extracted with mL). The combined organic layers were dried over sodium sulfate, the solvent was evaporated, and the residue was purified by column chromatography to give the title compound (hexane: diethyl ether = 60:: 1 ~ 50 1) (347.8 mg, 1.655 mmol, 83 %, to give a colorless oil). |
83% | With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In ethanol; water; toluene; at 80℃; for 22h;Inert atmosphere; | 3-bromobenzaldehyde (370.4 mg, 2.002 mmol), 2,6- dimethyl phenyl boronic acid (420.5 mg, 2.804 mmol), saturated aqueous sodium hydrogen carbonate solution (1M solution, 4 mL, 4.001 mmol) ethanol (2.2 mL) of and in a mixed solution of toluene (4 mL), tetrakis (triphenylphosphine) palladium (0) (114.9 mg, 0.099 mmol) was added, under an argon atmosphere and stirred for 22 hours at 80 C.. The reaction mixture was cooled, water (5 mL) and ethyl acetate (10 mL) was added and filtered over Celite (registered trademark). Was separated into aqueous and organic layers, the aqueous layer was extracted twice with ethyl acetate (20 mL), the combined organic layers were extracted with brine (30 mL), further sedge aqueous layer of ethyl acetate (20 and extracted with mL). The combined organic layers were dried over sodium sulfate, the solvent was evaporated, and the residue was purified by column chromatography (hexane: diethyl ether = 60: 1 to 50: 1) toRi purified title compound (347.8 mg, 1.655 mmol, 83%, colorless oil) was obtained. |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; at 100℃; for 16h; | To a degassed solution of 3-bromobenzaldehyde (500 mg, 2.70 mmol) , (2, 6-dimethylphenyl) boronic acid (608 mg, 4.05 mmol) , and Pd (PPh3) 4 (156 mg, 0.14 mmol) in dioxane (5 mL) was added K2CO3 (2N, 4.05 mL, 8.11 mmol) . The reaction was heated to 100. After 16 h, the mixture was poured into NH4Cl (sat, 25 mL) and extracted with EtOAc (2 x 25 mL) . The combined organic layers were dried over MgSO4 and concentrated. The resulting residue was purified by HPLC (ISCO 40 gram silica gel cartridge, 0 to 40EtOAc/Hex) to give the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium carbonate In ethanol; water; toluene for 21h; | 3.A Step A. Step A. 2,2',6'-Trimethyl-biphenyl-4-carboxylic acid methyl ester 2,6-Dimethyl boronic acid (13.7 g, 91 mmol) and 3-methyl benzoic acid methyl ester (20.9 g, 91 mmol) were dissolved in toluene (425 mL). Then ethanol (250 mL) and water (250 mL) were added followed by sodium carbonate (38.7 g, 365 mmole). The system was purged with nitrogen and then tetrakis triphenylphospine palladium (0) catalyst (10.5 g, 9 mmol) was added. The mixture was heated under nitrogen for 21 hours and filtered through celite. The cake was washed with a large amount of ethyl acetate, the combined filtrate was washed with water and brine, dried over anhydrous magnesium sulfate, and concentrated to give a solid. Flash chromatography of the residue over silica gel Merck-60 using a gradient of 0-20% ethyl acetate in hexane as the eluant, gave the title compound as a white solid (19.2 g, 83%). Anal. Calcd. for C17H18O2: C, 80.28; H, 7.13. Found: C, 80.37; H, 7.21. |
83% | With sodium carbonate In ethanol; water; toluene for 21h; | 10.A Example 10 N-(PYRIDIN-3-YLMETHYL)-10-[(2,2',6'-TRIMETHYL-1,1'-BIPHENYL-4-YL)CARBONYL]-10,11-DIHYDRO-5H-PYRROLO[2,1-C][1,4]BENZODIAZEPINE-3-CARBOXAMIDE Step A. 2,2',6'-Trimethyl-biphenyl-4-carboxylic acid methyl ester; 2,6-Dimethyl boronic acid (13.7 g, 91 mmol) and 3-methyl benzoic acid methyl ester (20.9 g, 91 mmol) were dissolved in toluene (425 mL). Then ethanol (250 mL) and water (250 mL) were added followed by sodium carbonate (38.7 g, 365 mmol). The system was purged with nitrogen and then tetrakis triphenylphospine palladium(0) catalyst (10.5 g, 9 mmol) was added. The mixture was heated under nitrogen for 21 hours and filtered through celite. The cake was washed with a large amount of ethyl acetate, the combined filtrate was washed with water and brine, dried over anhydrous magnesium sulfate, and concentrated to give a solid. Flash chromatography of the residue over silica gel Merck-60 using a gradient of 0-20% ethyl acetate in hexane as the eluant, gave the title compound as a white solid (19.2 g, 83%). Anal. Calcd. for C17H18O2: C, 80.28; H, 7.13. Found: C, 80.37; H, 7.21. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 4-chloro-2-methyl-indene; | EXAMPLE 2 Preparation of 2-Methyl-4-(2,6-dimethylphenyl) Indene from 2-Methyl-4-Bromoindene A flask is charged with palladium (II) acetate (60.8 mg, 0.27 mmol), 2-(dicyclohexylphosphino)-biphenyl (321 mg, 0.9 mmol), (2,6-dimethylphenyl) boronic acid (1.0 g, 6.6 mmol), and potassium phosphate (2.3 g, 10.8 mmol). The flask is filled with nitrogen before addition of dry deoxygenated toluene (14.8 g) and 2-methyl-4-bromoindene (1.0 g, 4.7 mmol) (prepared in analogous fashion to 2-methyl-4-chloroindene) via syringe. The mixture was stirred at 87-95 C. for 20 hours under nitrogen. Analysis of an aliquot by GC/MS revealed a 67% yield of desired product and 32% of starting 2-methyl-4-bromoindene. Work up and purification as described in Example 1 provided a 55% yield of 2-methyl-4-(2,6-dimethylphenyl) indene as 1:1 mixture of two olefin isomers. MS observed 234. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 1 Synthesis of 2-Methyl-4-(2,6-Dimethylphenyl)Indene Reaction Procedure A flask is charged with palladium (II) acetate (18.5 mg, 0.08 mmol), 2-(dicyclohexylphosphino)-2'-methyl biphenyl (94 mg, 0.26 mmol), (2,6-dimethylphenyl) boronic acid (1.7 g, 11.3 mmol, freshly recrystallized from Et2O/hexane) (synthesised according to literature, J.Am.Chem.Soc. (1960) 82:3053-3059), and potassium phosphate (3.1 g, 14.6 mmol). The flask is filled with nitrogen before addition of dry deoxygenated toluene (14 mL) and 2-methyl-4-chloroindene (1.3 g, 7.9 mmol) (synthesised according to U.S. Pat. No. 5,789,634) via syringe under nitrogen. The mixture was stirred at 100 C. for 20 hours under nitrogen. Analysis of an aliquot by GC/MS revealed a 66% yield of desired product and 33% of starting 2-methyl-4-chloroindene. The reaction was cooled to ambient temperature, diluted with diethyl ether and washed with aqueous saturated sodium bicarbonate. The organic phase was dried over sodium sulfate, filtered and evaporated in vacuo. The residue was purified by chromatography on silica gel eluted with hexane to afford 0.9 grams (49% isolated yield) of 2-methyl-4-(2,6-dimethylphenyl)indene as a pale yellow waxy solid, a 1:1 mixture of the two olefin isomers by proton NMR. Data: TLC Rf0.3 (hexane); observed M+234, calculated 234; 1H NMR (250 MHz, CD2Cl2) 7.35-7.13 (m, 5H), 6.96 (d, 0.5H), 6.84 (d, 0.5H), 6.81 (dd, 0.5H), 5.99 (br t, 0.5 H), 3.39 (s, 1H), 2.89 (s, 1H), 2.09 (s, 3H), 1.97 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene;Heating / reflux; | A mixture of 3-chloro-6-methoxy-pyridazine (1.44 g, 10 mmol), 2,6-methyl-phenyI boronic acid (1.73 g, 11.5 mmol), sodium carbonate (2 M aqueous solution, 10.5 ml, 21 mmol), ethanol (2 ml) and Pd(PPh3)4 (232 mg, 0.2 mmol) is refluxed in toluene (60 ml) overnight and then cooled to room temperature. EtOAc (20 ml) is added to the mixture and the organic layer is separated. The organiclayer is washed with water, dried, and solvent removed. The crude product is purified by flash silica gel column (Hexanes/EtOAc 4:1) to give 3-(2,6-dimethyl-phenyl)-6-methoxy-pyridazine. .H NMR: (CDC13) 7.21-7.30 (m, 2H), 7.12 (d, 2H), 7.03 (d, 2H), 4.20 (s, 3H), 2.05 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nitrogen; In ethyl acetate; toluene; | EXAMPLE 207 'N-(2,2',4,6,6'-Pentamethyl-1,1'-biphenyl-3-yl)-3-[(phenylsulfonyl)amino]thiophene-2-carboxamide Step One: To a solution of <strong>[82842-52-2]3-bromo-2,4,6-trimethylaniline</strong> (1.07 g, 5.0 mmol) and 2,6-dimethylphenyl boronic acid (1.5 g, 10 mmol) in toluene (10 mL) was added potassium phosphate, tribasic (3.2 g, 15 mmol) and the resulting mixture was deoxygenated by passing a stream of nitrogen for approximately 10 minutes. 2-Dicyclohexylphosphino-2,6-dimethoxy-1,1'biphenyl (0.164 g, 0.4 mmol) and tris(dibenzylidineacetone)dipalladium(0) (92 mg, 0.1 mmol) were added together in one portion, and nitrogen bubbling continued for approximately 2 minutes. The mixture was then heated in an oil bath at 110 C. under nitrogen overnight. The mixture was cooled, concentrated and passed through a pad of course silica gel. The resulting residue was purified on silica using 14:1 to hexanes to ethyl acetate. The residue from this operation was then vacuum distilled (Kugelrohr, 100 C., approximately 1 mtorr) to give the desired biphenyl (155 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; lithium chloride;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; ethamol; water; at 90℃; for 15.0h; | Production Example 13 In an atmosphere of nitrogen, a mixture of <strong>[107947-17-1]methyl 3-bromo-4-chlorobenzoate</strong>, (2,6-dimethylphenyl)boronic acid, lithium chloride, sodium carbonate, water, ethanol, dimethoxyethane and tetrakis(triphenylphosphine)palladium was stirred at 90C for 15 hours, thereby obtaining methyl 6-chloro-2',6'-dimemylbiphenyl-3-carboxylate. Lithium aluminum hydride was added under ice-cooling to a THF solution of the resulting methyl 6-chloro-2',6'-dimethylbiphenyl-3-carboxylate, followed by warming up to room temperature and stirring for 2 hours to obtain (6-chloro-2',6'-dimethylbiphenyl-3-yl)methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 85% 2: 3% | With potassium phosphate; R-Phos; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane at 100℃; for 0.333333h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium tetrachloropalladate(II); cataCXium F sulf; potassium carbonate In water at 100℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium tetrachloropalladate(II); cataCXium F sulf; potassium carbonate In water at 100℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tris-(dibenzylideneacetone)dipalladium(0); potassium phosphate monohydrate; 2-(2-methoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole In 1,4-dioxane at 110℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | To a solution of <strong>[54915-31-0]methyl 3-(benzyloxy)-5-hydroxybenzoate</strong> (3.10 g, 12.0 mmol) and N-ethyldiisopropylamine (2.51 mL, 14.4 mmol) in dichloromethane (30 mL) was added dropwise trifluoromethanesulfonic anhydride (2.22 mL, 13.2 mmol) under ice-cooling, and the mixture was stirred at the same temperature for 1 hr. The reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was dissolved in 1,2-dimethoxyethane (40 mL), and 2,6-dimethylphenylboronic acid (2.25 g, 15.0 mmol), tripotassium phosphate (3.82 g, 18.0 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.693 g, 0.600 mmol) were added. The reaction mixture was stirred under an argon atmosphere at 80C for 15 hr. The reaction mixture was concentrated under reduced pressure, and water was added to the residue. The mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-20% ethyl acetate/hexane) to give the title compound (3.60 g, yield 87%) as a yellow oil. MS m/z 347 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; copper diacetate; In dichloromethane; at 20℃; for 48h;Molecular sieve; | A screw-cap test tube containing molecular sieves (4A) and a solution of 3- methyl-lH-pyrazole-4-carbaldehyde (100 mg, 0.91 mmol), 2,6-dimethylphenylboronic acid (150 mg, 1 mmol), copper(II) acetate (247 mg, 1.36 mmol) and pyridine (147 mu, 1.8 mmol) in dry dichloromethane (4.5 mL) is shaked at room temperature for 48 hr. The mixture is filtered over celite, washed with methanol and the solvent evaporated in vacuo. Resulting product is purified by silica gel using normal phase Isco chromatography eluting with hexane: acetone (gradient from 5 to 30% in acetone) to give 67 mg of the title compound. MS (m/z): 215 (M+l) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; In tetrahydrofuran; for 16.0h;Inert atmosphere; Reflux; | General procedure: A typical procedure is given for the reaction represented by Entry 8 in Table 1. Ligand 2e (6 mg, 0.01 mmol), Pd2(dba)3 (5 mg, 0.005 mmol), 2-methylnaphthyl-1-boronic acid (223 mg, 1.2 mmol), Cs2CO3 (975 mg, 3 mmol) were introduced to a flask under N2 gas. 1-bromo-2-methylnaphthalene (221 mg, 1 mmol) was added into the flask, followed by addition of THF (5 ml) by a syringe. The mixture was stirred under reflux for 24 h, under ambient pressure of N2. The solvent was then removed under reduced pressure. The resultant residual mixture was diluted with H2O (10 ml) and Et2O (10 ml), followed by extraction twice with Et2O. The organic extract was collected and stripped of solvent under vacuum. The product was isolated by column chromatography on silica eluting with hexane/ethyl acetate to give 276 mg (98%) of 2,2'-dimethyl-1-1'-binaphthalene as a solid, which was verified by GC/MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With chloro[(1,2,3-n)-3-phenyl-2-propenyl][1,3-bis(2,7-dicyclooctylnaphthalen-1-yl)-imidazolin-2-ylidene] palladium(II); potassium <i>tert</i>-butylate In toluene at 20℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With potassium carbonate In 1,2-dimethoxyethane; water at 100℃; for 3h; Microwave irradiation; Inert atmosphere; | Intermediate 27{(S)-6-[(R)-4-(2,6-Dimethyl-phenyl)-indan-1 -yloxy1-2,3-dihydro-benzofuran-3-yl)-acetic acid methyl esterStep 1 : (S)-4-(2,6-dimethyl-phenyl)-indan-1 -olTetrakis(triphenylphosphine)palladium(0) (0.14 g) is added to a m icrowave vial charged with (S)-4-bromo-2,3-dihydro-1 H-inden-1 -ol (0.50 g), K2C03 (0.97 g), 2,6- dimethylphenylboronic acid (0.70 g), 1 ,2-dimethoxyethane (10 mL), and water (2.5 mL) under Ar atmosphere. The vial is sealed and the mixture is stirred at 100 °C for 3 h in a microwave oven. The mixture is diluted with water and extracted with ethyl acetate. The combined organic extract is washed with brine, dried (Na2S04), and concentrated. The residue is chromatographed on silica gel (heptane/ethyl acetate) to afford the title compound as an oil which crystallizes upon standing. Yield: 0.15 g (27% of theory); LC (method 4): tR = 1 .93 min; Mass spectrum (EST): m/z = 221 [M+H-H20]+. |
27% | With potassium carbonate In 1,2-dimethoxyethane; water at 100℃; for 3h; Microwave irradiation; Inert atmosphere; Sealed tube; | 27.1 Intermediate 27{(S)-6-[(R)-4-(2,6-Dimethyl-phenyl)-indan-1-yloxy]-2,3-dihydro-benzofuran-3-yl}-acetic acid methyl ester Step 1: (S)-4-(2,6-dimethyl-phenyl)-indan-1-olTetrakis(triphenylphosphine)palladium(0) (0.14 g) is added to a microwave vial charged with (S)-4-bromo-2,3-dihydro-1H-inden-1-ol (0.50 g), K2CO3 (0.97 g), 2,6-dimethylphenylboronic acid (0.70 g), 1,2-dimethoxyethane (10 mL), and water (2.5 mL) under Ar atmosphere. The vial is sealed and the mixture is stirred at 100° C. for 3 h in a microwave oven. The mixture is diluted with water and extracted with ethyl acetate. The combined organic extract is washed with brine, dried (Na2SO4), and concentrated. The residue is chromatographed on silica gel (heptane/ethyl acetate) to afford the title compound as an oil which crystallizes upon standing. Yield: 0.15 g (27% of theory); LC (method 4): tR=1.93 min; Mass spectrum (ESI+): m/z=221 [M+H-H2O]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 80℃; for 6h;Inert atmosphere; | General procedure: A 1,4-dioxane solution (8 mL) of 1 (1.0 mmol), arylboronic acid 2 (1.3 equiv.), 2 M K2CO3 (1 mL per cross coupling), and Pd(PPh3)4 (5 mol%) was heated at 80 8C for 6 h. After cooling to room temperature, H2O was added and the reaction mixture was extracted with CH2Cl2. The organic layer was dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (pure n-heptane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.1% | Stage #1: 2-chloro-5-nitropyridine; 2,6-dimethylbenzene boronic acid With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) In 1,2-dimethoxyethane at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium carbonate In 1,2-dimethoxyethane; water at 80℃; for 3h; Inert atmosphere; | 90.i (i) 2-(2,6-Dimethylphenyl)-5-nitropyridine 2-Chloro-5-nitropyridine (1.0 g, 6.31mmol), 2,6-dimethylphenylboronic acid (1.42 g, 9.47mmol) and bis(di-tert-butyl(4-dimethylaminophenylphosphine)dichloropalladium(II) (0.044 g, 0.062mmol) were added to 1,2-dimethoxyethan(32ml), degassed and purged with nitrogen three times under reduced pressure. Under nitrogen atmosphere the mixture was stirred at room temperature for 30 minutes, 1M aqueous sodium carbonate (12 ml) was poured in, and the temperature was raised to 80°C. After the reaction at 80 °C for 3 hours, the mixture was cooled to room temperature and extracted with addition of ethyl acetate and water. The organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography gave the title compound (1.41 g, 98.1%). |
98.1% | Stage #1: 2-chloro-5-nitropyridine; 2,6-dimethylbenzene boronic acid With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) In 1,2-dimethoxyethane at 20℃; for 0.5h; Inert atmosphere; Stage #2: With sodium carbonate In 1,2-dimethoxyethane; water at 80℃; for 3h; | 51.i (i) 2-(2,6-Dimethylphenyl)-5-nitropyridine 2-Chloro-5-nitropyridine (1.0 g, 6.31mmol), 2,6-dimethylphenylboronic acid (1.42 g, 9.47mmol) and bis(di-tert-butyl(4-dimethylaminophenylphosphine)dichloropalladium(II) (0.044 g, 0.062mmol) were added to 1,2-dimethoxyethan (32ml), degassed and purged with nitrogen three times under reduced pressure. Under nitrogen atmosphere the mixture was stirred at room temperature for 30 minutes, 1M aqueous sodium carbonate (12 ml) was poured in, and the temperature was raised to 80°C. After the reaction at 80 °C for 3 hours, the mixture was cooled to room temperature and extracted with addition of ethyl acetate and water. The organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography gave the title compound (1.41 g, 98.1%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With (phthalocyaninato)iron(II); palladium diacetate; (S)-4-Isopropyl-2-[2-(toluene-4-sulfinyl)-phenyl]-4,5-dihydro-oxazole In N,N-dimethyl-formamide at 80℃; for 12h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With iodine; potassium carbonate; In acetonitrile; at 80℃; for 12h;Inert atmosphere; Schlenk technique; Sealed tube; | General procedure: Arylboronic acid 1 (0.5 mmol) and K2CO3 (1 mmol, 138.0mg) were added to a 20 mL Schlenk-tube equipped with amagnetic stir bar. The tube was evacuated twice and backfilledwith N2. MeCN (2 mL) and I2 (0.75 mmol, 191 mg)were added to the tube at r.t. under a stream of N2, and thetube was sealed and placed into a pre-heated oil bath at 80 Cfor 8-12 h. The resulting solution was cooled to r.t. and H2O(10 mL) was added. The aq layer was extracted with EtOAc (3 × 5 mL). For products 2s and 2t, HCl (1 M) was added tothe aq solution until pH 2 before extraction. The combinedorganic phase was dried over anhydrous Na2SO4, filteredand concentrated by rotary evaporation. Purification of theresidue by column chromatography on silica gel providedthe desired product 2a-v |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In water; N,N-dimethyl-formamide for 2h; Microwave irradiation; Inert atmosphere; Heating; | 1.2 Synthesis of 4-phenyl-6-(2,6-dimethylphenyl)pyrimidine (abbreviation: Hppm-dmp) Next, 1.6 g of 4-chloro-6-phenylpyrimidine synthesized in Step 1, 1.5 g of 2,6-dimethylphenylboronic acid, 1.8 g of sodium carbonate, 59 mg of PdCl2(PPh3)2, 20. mL of N,N-dimethylformamide (abbreviation: DMF), and 20 mL of water were put into a 100-mL round-bottom flask, and the air in the flask was replaced with argon. Then, heating was performed by irradiation with microwaves (2.45 GHz, 100 W) for 2 hours.An organic layer was extracted from the obtained mixture with the use of dichiorornethane, and was washed with water and saturated brine. Magnesium sulfate was added and gravity filtration was performed. A solvent in the obtained filtrate was distilled off, and the given residue was purified by flash column chromatography using a mixed solvent of ethyl acetate and hexane (ethyl acetate: hexane = 1:5) as adeveloping solvent, whereby 0.50 g of the objective substance, Hppm-dmp (abbreviation) was obtained (yield: 23 %, a pale yellow oily substance). A synthesis scheme of Step 2 is shown in (a-2) below. |
23% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In water; N,N-dimethyl-formamide for 2h; Inert atmosphere; Microwave irradiation; | 1.2 Synthesis of 4-phenyl-6- (2,6-dimethylphenyl) pyrimidine Next, 1.6 g of 4-chloro-6-phenylpyrimidine obtained in the above step 1,1.5 g of 2,6-dimethylphenylboronic acid,1.8 g of sodium carbonate, 59 mg of PdCl2 (PPh) 2,20 mL of N, N-dimethylformamide (abbreviation: DMF)20 mL of water was put into a 100 mL round bottom flask, The inside of the flask was replaced with argon.Thereafter, heating was performed by irradiating microwave (2.45 GHz, 100 W) for 2 hours. The organic layer was extracted from the resulting mixture by dichloromethane,The organic layer was washed with water and saturated brine,Magnesium sulfate was added and dried.The mixture was naturally filtered.The solvent of the filtrate was removed by distillation,The residue was purified by flash column chromatography using ethyl acetate: hexane = 1: 5 as developing solvent,0.50 g of the target Hppm-dmp was obtained (yield: 23%, pale yellow oil). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; water; toluene; at 100℃; for 1h;Microwave irradiation; | General procedure: AG10 vial in a Microwave 300 vessel was charged with 6-bromopyridinecarboxaldehyde,or <strong>[122918-25-6]6-bromopyridinecarbonitrile</strong>(1 eq), boronic acid (2 eq),Na2CO3 (4 eq), and Pd(PPh3)2Cl2(10 mol%). Toluene/EtOH/water/ (2/1/1 mL) were next added. The resulting mixturewas irradiated using the closed vessel mode at 100C for 60 min. The mixture wasthen extracted with dichloromethane, washed with a saturated solution of NaHCO3,dried over MgSO4, and concentrated by rota-evaporation under vacuum.The crude product was purified by flash chromatography, with a pentane /AcOEt (9/1to 7/3) as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With NHC-Pd(II)-Im; sodium hydroxide In tetrahydrofuran at 100℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With palladium diacetate; In water; toluene; | Example 39 Into a glass reaction vessel equipped with a cooling apparatus were added 0.0015 mmol of palladium acetate, 0.0030 mmol of 3,5-di-(tert-butyl)phenyl)phosphonium tetrafluoroborate, 0.3 mmol of trioctylmethylammonium chloride, 1.5 mmol of o-tolyl bromide, 1.65 mmol of 2,6-dimethylphenylboronic acid, 3.0 mmol of sodium carbonate, 6 mL of toluene and 1.5 mL of water. The resultant mixture was stirred with heating at 100 C. for 3 hours. The resultant reaction mixture was cooled down to room temperature, 20 mL of water was added, and the mixture was extracted with 20 mL of diethyl ether twice. The resultant organic layers were mixed, and dried over anhydrous magnesium sulfate, then, filtrated, to obtain a solution. This solution was concentrated, and purified by silica gel column chromatography, to obtain 2,4,2'-trimethylbiphenyl with a yield of 91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | With tris-(dibenzylideneacetone)dipalladium(0); potassium phosphate monohydrate; C30H25FeP In 1,4-dioxane at 100℃; for 48h; Sealed tube; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; for 4h;Reflux; Inert atmosphere; | A mixture of 2-bromobenzyl cyanide (12.3 g, 62.7 mmol, prepared by following theliterature procedure [3]), 2,6-(dimethylphenyl)boronic acid (11.2 g, 75.2 mmol), 125mL aqueous solution of Na2CO3 (2 M, 250 mmol), EtOH (50 mL), and Pd(PPh3)4(2.90 g, 2.51 mmol) in cyclopentyl methyl ether (CPME) (50 mL) was stirred atreflux under an inert atmosphere for 4 h. Upon consumption of 2-bromobenzylcyanide as judged by TLC analysis, the reaction mixture was cooled to roomtemperature, and the solvents were removed in vacuo. The organic materials werethen extracted with a mixture of Et2O-H2O (1:1). The organic extract was washedwith 5% aqueous NaOH followed by water and brine. After drying with MgSO4, thesolution was concentrated in vacuo to yield a crude residue, which was purified byflash column chromatography using hexane-EtOAc (98:2) as eluent to give 2-(2',6'-dimethyl-[1,1'-biphenyl]-2-yl)acetonitrile (S-1a) (9.72 g, 43.9 mmol) in 70% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water at 103℃; for 24h; Inert atmosphere; | Step 1: Preparation of 1-(2',6'-dimethyl-[1,1'-biphenyl]-2-yl)ethan-1-one (S-2): A mixture of 2-bromoacetophenone (2.98 g, 15.0 mmol), 2,6-dimethylphenyl)boronicacid (2.70 g, 18.0 mmol), 30 mL aqueous Na2CO3 (2 M, 60.0 mmol), EtOH (10 mL),and Pd(PPh3)4 (1.38 g, 1.2 mmol) in cyclopentyl methyl ether (CPME) (20 mL) wasstirred at reflux under an inert atmosphere for 24 h. The reaction mixture was cooledto rt and the solvents were removed in vacuo. The organic materials were thenextracted with a mixture of Et2O-H2O (1:1) and the organic extract was washed with5% aqueous NaOH followed by water and brine. After drying with MgSO4, thesolution was concentrated in vacuo to yield a crude residue, which was purified byflash column chromatography using hexane-EtOAc (98:2) as the eluent to afford 1-(2',6'-dimethyl-[1,1'-biphenyl]-2-yl)ethan-1-one (S-2, 2.86 g, 12.7 mmol) in 85%yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0) In tert-Amyl alcohol; water; toluene at 80 - 90℃; for 22h; Inert atmosphere; | 8.8.1 Preparation of 2,4-bis(2,6-dimethylphenyl)-6-nitroaniline A mixture of 200 ml of toluene, 20 ml of 2-methyl-2-butanol, 5.4 g (18.4 mmol) of 2,4- dibromo-6-nitroaniline, 5.5 g (36.8 mmol) of 2,6-dimethylphenylboronic acid, 9.7 g (45.9 mmol) of potassium phosphate, 10 ml of water, 0.2 g (0.218 mmol) oftris(dibenzylidenacetone)dipalladium and 0.34 g (0.828 mmol) of S Phos (2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl) were heated under nitrogen at 80°C for 6 h and then at 90°C for 16 h. After evapaporation of the solvent, the residue was crystalized from petrol ether having a temperature of 40°C. This gave 6.44 g (quant.) of a solid having a HPLC purity of 89%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In toluene; at 120℃; for 16h; | A mixture of <strong>[17823-40-4]4-bromo-2,3,5,6-tetrafluorobenzonitrile</strong> (1.0 g, 3.9 mmol), 2,6-dimethylphenylboronic acid (1.2 g, 8 mmol), Pd2(dba)3 (0.18 g, 0.2 mmol), SPhos(0.16 g, 0.4 mmol) and potassium phosphate (0.23 g, 10 mmol) in toluene (50 mL) was degassed and heated at about 120 C for about 16 hours. After being cooled to room temperature, the mixture was filtered, washed with toluene. The filtrate solution was loaded on flash column and using eluents of hexane/dichloromethane(1:0 to 4:1). The desired fraction was collected and concentrated slowly to give a colorless liquid (Compound 4) (0.35 g, in 32% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8 g | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; In water; toluene; for 12.0h;Reflux; | 10 g (44 mmol) of 4-bromo-8-quinolylquinoline (Monatshef te fiir Chemie (1991), 122(11), 935-41) were dissolved in 100 ml of toluene. 100 ml of water, 7.3 g (50 mmoles) of 2,6-dimethylphenyl group were addedBoric acid, 20.2 g (88 mmol) of hydrated potassium phosphate, 200 mg of palladium acetate and 750 mg of 2-dicyclohexylphosphino-2 ', 6'Dimethoxybiphenyl (= S-PH0S). After heating for 12 hours under reflux, the mixture was cooled, subjected to phase separation and steamingThe remaining solid was chromatographed on silica gel (heptane: ethyl acetate 10: 1). The material was recrystallized from toluene / acetonitrileOnce, 8.0 g (32 mmol) of 4- (2,6-dimethylphenyl) -8-hydroxyquinoline was obtained as a colorless solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In water; acetonitrile; for 6.5h;Inert atmosphere; Microwave irradiation; | Subsequently, 0.96 g of <strong>[38696-20-7]5-bromo-2-phenylpyrimidine</strong> obtained in the above step 1, 1.21 g of 2,6-dimethylphenylboronic acid, 0.87 g of sodium carbonate, 0.76 g of bis (triphenylphosphine) palladium (II) dichloride (Abbreviation: Pd (PPh 3) 2 Cl 2), 15 mL of water and 15 mL of acetonitrile were placed in a recovery flask equipped with a reflux tube and argon bubbling was carried out for 15 minutes. The reaction vessel was heated by irradiating microwave (2.45 GHz 100 W) for 3 hours. Here, 1.21 g of 2,6-dimethylphenylboronic acid, 0.87 g of sodium carbonate and 0.035 g of Pd (PP 3) 2 Cl 2 were placed in a flask and argon bubbling was carried out for 15 minutes. This reaction vessel was heated again by irradiating microwave (2.45 GHz 100 W) for 3 hours. Thereafter, the obtained mixture was suction filtered with water. The obtained solid was purified by flash column chromatography using toluene as a developing solvent to obtain the desired pyrimidine derivative Hppm 2-dmp (white powder, yield 64percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium phosphate; C22H23Br2N3Pd; In water; isopropyl alcohol; at 20℃; for 44h; | General procedure: A test tube was charged with aryl chlorides (0.5 mmol, 1 eq), arylboronic acid (0.75 mmol, 1.5 eq), K3PO4 (1 mmol, 2 eq), H2O (0.5 mL), isopropanol (0.5 mL) and catalyst (0.0005-0.001 mmol) and the mixture was then stirred at room temperature. After the reaction was finished, the mixture was extracted three times with CH2Cl2 (3 x 2mL), dried over Na2SO4, filtered, and the solvent was removed under vacuum. Further purification of the product was achieved by flash chromatography on a silica gel column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 100℃; for 16h;Inert atmosphere; | To a stirred solution of <strong>[1004294-58-9]6-bromo-5-chloropyridin-2-amine</strong> (5.0 g, 24.10 minol) in dioxane (60 mL) were added (2,6-dimethylphenyl)boronic acid (5.42 g, 36.15 minol) and 2M K3P04 solution (36.3 mL) under N2. Then Pd(PPh3)4 (2.8 g, 2.41 minol) was added, degassed and the reaction mixture was stirred at 100C for 16 h. Then the reaction mixture was cooled to rt, diluted withwater and extracted with EtOAc twice. Combined organic portion was washed with brine solution, dried over anhydrous Na2SO4 and concentrated. The residue was purified by flash column chromatography (12 g SiliCycle column, 14% EtOAc in Hexane elution) to afford Intermediate (10): as an off white solid. LC/MS, ESI-MS (k): 233.2. 1H NMR (300 MHz, CDCI3) O ppm 7.52 (d, J= 8.4 Hz, 1H), 7.21 -7.17 (m, 1H), 7.10-7.08 (m, 2H), 6.47 (d, J=8.7 Hz, 1H), 4.54 (brs, 2H), 2.06 (5, 3H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With palladium diacetate; potassium carbonate; triphenylphosphine; In methanol; acetonitrile; at 60℃; for 24h;Inert atmosphere; | To a flask charged with <strong>[39919-65-8]3,6-dibromo-2-methylpyridine</strong> (2.50 g, 9.96 mmol), 2,6-dimethylphenyl boronic acid (1.75 g, 11.7 mmol), palladium acetate (112 mg, 0.498 mmol), triphenylphosphine (261 mg, 0.996 mmol), and potassium carbonate (2.75 g, 19.9 mmol) under a N2 atmosphere was added acetonitrile (75 25 mL) and methanol (38 mL) at room temperature. The flask was attached to a refluxcondenser and heated to 60 °C. After 24 h, the crude reaction mixture was cooled to rt, and the volatiles were removed under reduced pressure. The resulting residue was dissolved in dichloromethane, and the organic layer was washed with water and brine. The washed organic layer was dried over Na2S04, filtered and concentrated. The resulting residue was purified via silica gel chromatography, eluted with hexane: CH2CI2 = 5:1, to afford the product as a white solid in 43percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 24h;Reflux; Inert atmosphere; | Dissolve <strong>[405174-97-2]3-bromo-2-pyridinecarboxaldehyde</strong> (125 mg, 0.672 mmol) in toluene (2 mL) and add a solution of 2,6-dimethylphenylboronic acid (120 mg, 0.806 mmol) in ethanol (1 mL) while stirring, then add 2M Sodium carbonate solution (3 mL) followed by Pd[P(Ph)3]4 (100 mg, 0.0806 mmol). After the mixture was evacuated for N2 three times, it was refluxed for 24 h under N2 atmosphere. After allowing to cool, the layers were separated and the organic layer was separated. The aqueous layer was extracted twice with ether. The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated by filtration. The residue was purified by column chromatography to give the title compound as a white solid (51 mg; Yield 36%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: 2-Bromo-6-methoxynaphthalene With tripotassium phosphate tribasic In 1,4-dioxane; water monomer for 0.333333h; Inert atmosphere; Sonication; Stage #2: 2,6-dimethylbenzene boronic acid With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; Palladium(0) bis(dibenzylideneacetone) In 1,4-dioxane; water monomer at 101℃; for 12h; Inert atmosphere; | |
21% | With (2-methoxyphenyl)diphenylphosphine; palladium diacetate; Cs2CO3 In 1,4-dioxane at 100℃; for 16h; Inert atmosphere; Schlenk technique; | 4.3. General procedure for the palladiumcatalyzedSuzuki-Miyaura cross-couplingreactions General procedure: In a Schlenk tube, in an inert atmosphere, a solutionof [Pd(OAc)2] in 1,4-dioxane, a solution ofthe ligand 1 (ratio Pd/1 1/1) in 1,4-dioxane, arylhalide (0.5 mmol), aryl boronic acid (0.75 mmol),Cs2CO3 (0.325 g, 0.75 mmol), decane (0.025 mL, internalreference) and a complementary amount of1,4-dioxane, so that the total reaction volume was2.0 mL, were introduced. The reaction mixture wasthen heated at 100 °C. After cooling to room temperature,a small amount (0.5 mL) of the resulting solutionwas passed through a Millipore filter and analyzedby GC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With C27H39Br2N3Pd; potassium hydroxide; In isopropyl alcohol; at 82℃; for 0.166667h; | General procedure: A two-necked 25.0mL flask fitted with a reflux condenser and septum was charged with aryl halide (1.0mmol), phenylboronic acid (1.2mmol), KOH (2.0mmol), diethyleneglycol-di-n-butylether (0.6mmol, internal standard), and the palladium-pyridine catalyst (0.01mol %) in isopropyl alcohol (1.0mL) was added. The mixture was heated to 82C under an air atmosphere. The conversion was monitored by gas chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 6h;Inert atmosphere; | to with magnetic rotor and the condensation of the 100 ml dry three-mouth bottle is sequentially added in the intermediate 4 (6.90 g, 30 mmol, 1.0 equivalent), 2, 5 - dimethyl phenyl boronic acid (3.84 g, 31.5 mmol, 1 . 05 equivalent), Pd (PPh3)4(1.04 G, 0.9 mmol, 0 . 03 equivalent), K2CO3(8.29 G, 60 mmol, 2.0 equivalent), replacing the nitrogen three times, under the protection of nitrogen added to the 1, 4 - dioxane (30 ml) and H2O (15 ml). The oil bath temperature is raised to 100 C stirring reaction 6.0 hours, cooling to room temperature, for 30 ml ethyl acetate extraction three times, using anhydrous Na2SO4Drying the organic phase, then filtered, distilled under reduced pressure, the solvent is removed, dry sample, using silica gel column chromatography column to carry out the separation and purification, eluent petroleum ether/ethyl acetate=20 is: 1, to obtain white solid 5.29 g, yield 69%. Directly used for the next step reaction. |
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 6h;Inert atmosphere; | Intermediate 4 (6.90 g, 30 mmol, 1.0 eq.) was added sequentially to a 100 mL dry three-necked flask with a magnetic rotor and a condensing tube.2,5-Dimethylbenzeneboronic acid (3.84 g, 31.5 mmol, 1.05 equivalent),Pd(PPh3)4 (1.04g, 0.9mmol, 0.03 equivalents),K2CO3 (8.29g, 60mmol, 2.0 equivalents),Swap three times with nitrogen, was added 1,4-dioxane (30mL) and H2O (15mL) under nitrogen.The temperature of the oil bath was raised to 100 C and the reaction was stirred for 6.0 hours.After cooling to room temperature, it was extracted three times with 30 mL of ethyl acetate.Then, filtration, distillation under reduced pressure, removal of the solvent, dry-loading, separation and purification using a silica gel column chromatography column, the eluent is petroleum ether / ethyl acetate = 20:1,5.29 g of a white solid were obtained in a yield of 69%. Used directly in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In 1,4-dioxane; water at 100℃; for 3h; Inert atmosphere; | 1-([1,1':4',1''-terphenyl]-3-yl)-2-phenylethane-1,2-dione(T-2) General procedure: A dried radius flask was charged with T-1 (115.2 mg, 0.4 mmol, 1.0 equiv.),4-biphenylboronic acid (158.4 mg, 0.8 mmol, 2.0 equiv.), Pd(PPh3)2Cl2(28.08 mg, 0.04 mmol, 10 mol %), K2CO3 (165.6mg, 1.2 mmol, 3 equiv.), H2O (100 μL) and 1,4-dioxane (4.0 mL). Themixture was stirred at 100 °C for 3 h under nitrogen. Upon completion of thereaction as monitored by TLC, the reaction was allowed to cool to roomtemperature, and extracted with ethyl acetate (20 mL × 3). The organic phasewas collected and washed with brine, dried over with anhydrous Na2SO4,ltered, and concentrated. The filtrate was evaporated under reduced pressure,and the residue was purified by column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent to afford the desired product T-2 (136.4 mg, 94 %) as yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); potassium methanolate In tetrahydrofuran at 70℃; for 24h; Schlenk technique; Sealed tube; | 29 Example 29 In the glove box, Add 2,6-dimethylphenylboronic acid (1mmol, 150.0mg) to a 50mL Schlenk bottle with a stir bar in order, potassium methoxide (2 mmol, 2 equivalents, 140.2 mg), Cu(IPr)Cl (0.03 mmol, 0.03 equivalents, 14.6 mg), 5 mL of solvent tetrahydrofuran. remove the capped Schlenk bottle from the glove box, fully evacuate, fill the reaction system with carbon dioxide and seal it well, and then stir the reaction mixture at 70 ° C. for 24 hours. After cooling to room temperature, it was acidified by adding 1 mol / L hydrochloric acid, and extracted with ethyl acetate, and washed once with brine. The organic phase was collected and concentrated in vacuo. The liquid mixture was dropped on a silica gel column and purified by column chromatography. As petroleum ether / ethyl acetate, the desired product 2,6-dimethylbenzoic acid was obtained with a yield of 88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With palladium diacetate; potassium carbonate In toluene at 100℃; for 72h; |
[ 85199-06-0 ]
2,5-Dimethylphenylboronic acid
Similarity: 0.90
[ 55499-44-0 ]
2,4-Dimethylphenylboronic acid
Similarity: 0.90
[ 85199-06-0 ]
2,5-Dimethylphenylboronic acid
Similarity: 0.90
[ 55499-44-0 ]
2,4-Dimethylphenylboronic acid
Similarity: 0.90
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Code | Phrase |
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P272 | Contaminated work clothing should not be allowed out of the workplace. |
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P378 | |
P380 | Evacuate area. |
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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 |
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P402 | Store in a dry place. |
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Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
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H203 | Explosive; fire, blast or projection hazard |
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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 |
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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 |
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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 |
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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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