* 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.
Reference：
[1] European Journal of Medicinal Chemistry, 2015, vol. 101, p. 780 - 789
[2] Patent: CN104262238, 2016, B,
7
[ 5720-05-8 ]
[ 120-92-3 ]
[ 1671-77-8 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 16, p. 5347 - 5351
8
[ 371-67-5 ]
[ 5720-05-8 ]
[ 106-44-5 ]
[ 446-65-1 ]
Yield
Reaction Conditions
Operation in experiment
40%
Stage #1: at 40℃; Inert atmosphere; Sealed tube Stage #2: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran at 0 - 23℃; for 2 h;
2, 2, 2-Trifluoro-l-(p-tolyl)ethanol and 1, 1, 1, 4, 4, 4-hexafluoro-3-(p-tolyl)butan-2-ol [0146] Procedure E: / Tolylboronic acid (136 mg, 1 mmol) was added to a 20 mL Biotage microwave vial equipped with a stir bar. The vial was sealed and purged with argon three times. The diazo stock solution (8 mL, 0.5 M) was added, and the reaction was stirred at 40 °C overnight. The solvent was evaporated from the crude reaction mixture under reduced pressure, and the solid was redissolved in THF (5 mL), then treated with a solution of 2 N NaOH (6 M)/30percent H2O2 (2: 1 v/v, 2 mL) at 0 °C. The reaction mixture was allowed to warm to RT and stirred for 2 h. The phases were separated, and the aqueous phase was extracted with Et20 (2 X 5 mL). The organic phases were combined, dried (MgSC^), concentrated, and purified by column chromatography to obtain 2,2,2-trifluoro-l-(p-tolyl)ethanol (43 mg, 40percent) and 1, 1, 1,4,4,4- hexafluoro-3-(p-tolyl)butan-2-ol (40 mg, 21percent) along with / methylphenol (38 mg, 14percent).
Reference：
[1] Journal of Medicinal Chemistry, 2012, vol. 55, # 9, p. 4407 - 4424
[2] European Journal of Medicinal Chemistry, 2013, vol. 61, p. 26 - 40
11
[ 2042-37-7 ]
[ 5720-05-8 ]
[ 64113-85-5 ]
Yield
Reaction Conditions
Operation in experiment
94%
With potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene
Example 2 165 mmol of bromobenzonitrile, 247 mmol of 4-methylphenylboronic acid, 330 mmol of potassium carbonate are heated with 0.2 mol percent of trans-di-acetato-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) in 300 ml of xylene for 16 hours at 130° C. The reaction solution is distilled after aqueous workup. Yield: 94percent of 2-cyano-4-methylbiphenyl.
Reference：
[1] Patent: US5559277, 1996, A,
12
[ 873-32-5 ]
[ 5720-05-8 ]
[ 64113-85-5 ]
Yield
Reaction Conditions
Operation in experiment
73%
With potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene
Example 7 157 mmol of 2-chlorobenzonitrile, 236 mmol of 4-methylphenylboronic acid, 314 mmol of potassium carbonate are heated with 0.2 mol percent of trans-di-acetato-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) in 300 ml of xylene for 16 hours at 130° C. The reaction solution is recrystallized after aqueous workup. Yield: 73percent of 2-cyano-4-methylbiphenyl.
Reference：
[1] Patent: US5559277, 1996, A,
13
[ 2042-37-7 ]
[ 5720-05-8 ]
[ 64113-85-5 ]
Yield
Reaction Conditions
Operation in experiment
80%
With sodium carbonate In methanol; water; toluene
Example 2 2M Sodium carbonate solution (200 ml) was added to a stirred mixture of 4-methylphenylboronic acid (30 g), 2-bromobenzonitrile (36.4 g), palladium (II) chloride (0.4 g), methanol (200 ml) and toluene (200 ml) at 5°C. The temperature rose to approximately 20°C and a solid precipitated. The reaction mixture was then heated at reflux for 2 hours. The reaction mixture was allowed to cool and water (100 ml) was added, followed by diatomaceous earth (5 g). The mixture was stirred for 15 minutes, then filtered through diatomaceous earth. The organic phase of the filtrate was separated and washed with 2M sodium carbonate solution and then water. The organic phase was then filtered and the filtrate evaporated. The resultant solid was recrystallized from petroleum ether (b.p. 110-120°C) to give 4--methylbiphenyl-2-carbonitrile (in 80percent yield) identical to that obtained in Example 1.
Reference：
[1] Journal of Organometallic Chemistry, 2007, vol. 692, # 20, p. 4244 - 4250
[2] Journal of Organometallic Chemistry, 2007, vol. 692, # 20, p. 4244 - 4250
17
[ 108-88-3 ]
[ 17933-03-8 ]
[ 5720-05-8 ]
Reference：
[1] Journal of Organometallic Chemistry, 2007, vol. 692, # 20, p. 4244 - 4250
18
[ 5720-05-8 ]
[ 68162-47-0 ]
Reference：
[1] Organic Letters, 2004, vol. 6, # 13, p. 2085 - 2088
[2] Russian Chemical Bulletin, 2004, vol. 53, # 2, p. 370 - 375
19
[ 128-08-5 ]
[ 5720-05-8 ]
[ 68162-47-0 ]
Reference：
[1] Russian Chemical Bulletin, 2004, vol. 53, # 2, p. 370 - 375
20
[ 5720-05-8 ]
[ 4334-88-7 ]
Reference：
[1] Chemical Communications, 2014, vol. 50, # 52, p. 6886 - 6889
[2] Chemistry - A European Journal, 2015, vol. 21, # 45, p. 16083 - 16090
[3] Inorganic Chemistry, 2017, vol. 56, # 16, p. 9765 - 9771
21
[ 5720-05-8 ]
[ 7697-37-2 ]
[ 80500-27-2 ]
Reference：
[1] Journal of the American Chemical Society, 1932, vol. 54, p. 4415 - 4424
[2] , Gmelin Handbook: B: B-Verb.13, 4.7.2.5, page 209 - 219,
22
[ 5720-05-8 ]
[ 80500-27-2 ]
Reference：
[1] Journal of the American Chemical Society, 1932, vol. 54, p. 4415,4418
23
[ 5720-05-8 ]
[ 85107-55-7 ]
Reference：
[1] Journal of Chemical Research, 2014, vol. 38, # 12, p. 719 - 721
24
[ 5720-05-8 ]
[ 124750-53-4 ]
Reference：
[1] Patent: WO2013/78237, 2013, A1,
[2] Journal of Chemical Sciences, 2014, vol. 126, # 1, p. 205 - 212
[3] Journal of Chemical Sciences, 2014, vol. 126, # 1, p. 205 - 212
25
[ 5720-05-8 ]
[ 114772-40-6 ]
Reference：
[1] Journal of Medicinal Chemistry, 1994, vol. 37, # 7, p. 897 - 906
26
[ 21190-87-4 ]
[ 5720-05-8 ]
[ 86696-72-2 ]
Yield
Reaction Conditions
Operation in experiment
90%
Stage #1: With sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 100℃; for 2 h; irradiated in a microwave Stage #2: With hydrogenchloride In water
A mixture of 6-bromo- pyridine-2-carboxylic acid (202 mg, 1 mmol), 4-methylphenylboronic acid ( 163 mg, 1.2 mmol), and Pd(PPh3)4 (25 mg) in saturated aq. NaHC03 solution (3 mL) and DME (3 mL) was irradiated in a microwave on a Biotage Smith Synthesizer at 100 °C for 2 hrs. TLC showed the reaction was completed. The mixture was filtered and washed with water (2 x 50 mL) and ether (2 x 50 mL). The organic and aqueous layers were separated. The pH of the aqueous portion was adjusted to about 1 with 1 N aq. HCI solution. The aqueous layer was then extracted with ethyl acetate (3 x 60 mL). The combined organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was evaporated to give the title compound ( 191 mg, 90percent yield).
90%
Stage #1: With sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 100℃; for 2 h; Microwave Stage #2: With hydrogenchloride In water
Step A. 6-p-Tolyl-pyridine-2-carboxylic acid. A mixture of 6-bromo-pyridine-2-carboxylic acid (202 mg, 1 mmol), 4-methylphenylboronic acid (163 mg, 1.2 mmol), and Pd(PPh3)4 (25 mg) in saturated aq. NaHCO3 solution (3 mL) and DME (3 mL) was irradiated in a microwave on a Biotage Smith Synthesizer at 100° C. for 2 hrs. TLC showed the reaction was completed. The mixture was filtered and washed with water (2*50 mL) and ether (2*50 mL). The organic and aqueous layers were separated. The pH of the aqueous portion was adjusted to about 1 with 1 N aq. HCl solution. The aqueous layer was then extracted with ethyl acetate (3*60 mL). The combined organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was evaporated to give the title compound (191 mg, 90percent yield).
To a mixture of 4-tolylboronic acid (38 g, 0.28 mol), 3-bromopyridine (44 g, 0.28 mol), Na2CO3 (200 g) in toluene (500 ml) and water (500 ml) was added Pd(PPh3)4 (16 g, 0.014 mol), and refluxed for 16 h. The reaction mixture was cooled, and the separated organic layer was washed with water and brine, and dried. The solvent was removed to give 4-(3-pyidyl)toluene s (42 g, 90percent). To a mixture of 4-(3-pyridyl)toluene (35 g, 0.207 mol) in pyridine (400 ml) and water (400 ml) was added KMnO4 (163 g, 1.03 mol) in portions and refiuxed for 12 h. The reaction mixture was filtered through celite and acidified with cone. HCl. The product was washed with water and dried to give 4-(3pyridyl)benzoic acid (32 g, 76percent) as a white solid.
Reference：
[1] Patent: US2003/212012, 2003, A1,
28
[ 5720-05-8 ]
[ 4385-75-5 ]
Reference：
[1] European Journal of Medicinal Chemistry, 2015, vol. 101, p. 780 - 789
Reference：
[1] Journal of the American Chemical Society, 2009, vol. 131, # 47, p. 17500 - 17521
32
[ 5720-05-8 ]
[ 142-71-2 ]
[ 285983-48-4 ]
Yield
Reaction Conditions
Operation in experiment
50%
With pyridine In dichloromethane
Example 2 Synthesis of 1-(5-tert-Butyl-2-p-tolyl-2H-pyrazol-3-yl)-3-[4-(2-morpholin-4-yl-ethoxy)-naphthalen-1-yl]-urea: The title compound was prepared as described in the final step of Example 1 from 1-(5-tert-butyl-2H-pyrazol-3-yl)-3-[4-(2-morpholin-4-yl-ethoxy)-naphthalen-1-yl]-urea (0.022 g, 0.050 mmol), and p-tolylboronic acid (0.014 g, 0.1 mmol), using copper (II) acetate (0.014 g, 0.075 mmol), pyridine (0.01 mL, 0.1 mmol), molecular sieves (4 Å activated, 0.030 g) and methylene chloride (2 mL). The title compound was obtained as a yellow-white solid (0.013 g, 50percent), mp 144 -146° C; 1H NMR (DMSO) 1.26(s, 9H), 2.36(s, 3H), 2.53(t, 4H) 2.82(t, 2H), 3.52(t, 4H), 4.23(t, 2H), 6.32(s, 1H), 6.94(d, 1H), 7.33(d, 1H), 7.42(d, 1H), 7.54(m, 3H), 7.90(d, 1H), 8.15(d, 1H), 8.18(d, 1H) 8.82(s, 1H), 8.96(s, 1H); MS (CI) 528(M++H).
Reference：
[1] Journal of Chemical Research, 2014, vol. 38, # 12, p. 719 - 721
36
[ 5720-05-8 ]
[ 677010-20-7 ]
Reference：
[1] Chemical Communications, 2011, vol. 47, # 5, p. 1452 - 1454
37
[ 1072-97-5 ]
[ 5720-05-8 ]
[ 503536-74-1 ]
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 18, p. 4500 - 4505
[2] Journal of Medicinal Chemistry, 2008, vol. 51, # 15, p. 4724 - 4729
38
[ 13534-97-9 ]
[ 5720-05-8 ]
[ 170850-45-0 ]
Reference：
[1] Journal of the American Chemical Society, 2013, vol. 135, # 23, p. 8436 - 8439
[2] Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 15, p. 3057 - 3061
39
[ 5350-93-6 ]
[ 5720-05-8 ]
[ 170850-45-0 ]
Reference：
[1] New Journal of Chemistry, 2017, vol. 41, # 24, p. 15420 - 15432
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 100℃; for 0.666667h;Sealed vial;
To a 350 mL high-pressure vial was added <strong>[55666-42-7]ter<strong>[55666-42-7]t-butyl 2-bromobenzoate</strong></strong> (5.142 g, 20.0 mmol), p-tolylboronic acid (4.08 g, 30.0 mmol), Pd(PPh3)4 (3.47 g, 3.0 mmol), potassium carbonate (8.29 g, 60.0 mmol) and dioxane with water (4:1, 200 mL). The mixture was degassed for 5 min and sealed. The mixture was heated at 100 C. for 40 min wherein analytical HPLC analysis indicated the completion of the reaction. The mixture was filtered through Celite and MeOH was used to wash the Celite pad. The solvent was removed and the crude was purified by flash chromatography (AcOEt/Hexane 0->30%) to obtain the title compound.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 0.75h;Sealed tube;
To a 350 mL high-pressure vial was added <strong>[55666-42-7]ter<strong>[55666-42-7]t-butyl 2-bromobenzoate</strong></strong> (5.142 g, 20.0 mmol), p-tolylboronic acid (4.08 g, 30.0 mmol), Pd(PPh3)4(3.47 g, 3.0 mmol), potassium carbonate (8.29 g, 60.0 mmol) and dioxane with water (4:1, 200 mL). The mixture was degassed for 5 min and sealed. The mixture was heated at 100C for 40 min wherein analytical HPLC analysis indicated the completion of the reaction. The mixture was filtered through Celite and MeOH was used to wash the Celite pad. The solvent was removed and the crude was purified by flash chromatography (AcOEt /Hexane 0->30%) to obtain the title compound.
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,2-dimethoxyethane; at 90℃;
EXAMPLE 28 COMPOUND 28: N1-(3-methyl-pyridin-2-ylmethyl)-N1-(3-p-tolyl-pyridin-2-ylmethyl)-butane-1,4-diamine (HBr salt) To a stirred degassed solution of <strong>[405174-97-2]3-bromo-2-pyridinecarboxaldehyde</strong> (198 mg, 1.06 mmol) and 4-methylbenzene boronic acid (152 mg, 1.12 mmol) in DME/THF (3.5 mL, 2.5:1) were added a 2 M Na2CO3 solution (0.9 mL) and Pd(PPh3)4 (63 mg, 0.055 mmol). The reaction mixture was flushed with Ar and maintained under Ar while being heated at 90 C. overnight. The mixture was then cooled and diluted with EtOAc (40 mL) and brine (30 mL). The organic layer was washed with brine (1*30 mL), dried (Na2SO4), filtered and concentrated. Purification of the resultant oil by column chromatography with silica gel (Hexanes/EtOAc, 2:1) afforded 3-p-tolyl-pyridine-2-carbaldehyde (161 mg, 77%) as a yellow oil. 1H NMR (CDCl3) delta 2.43 (s, 3H), 7.25-7.28 (m, 4H), 7.53 (dd, 1H, J=9, 6 Hz), 7.79 (dd, 1H, J=9, 1 Hz), 8.80 (dd, J=3, 1 Hz), 10.09 (s, 1H).
tert-butyl 4'-methyl[1,1-biphenyl]-3-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium carbonate; In 1,2-dimethoxyethane;
Step 1 tert-butyl 4'-methyl[1,1 biphenyl]-3-carboxylate A mixture of 4-methylphenylboronic acid (0.65 g, 4.3 mmol), t-butyl-<strong>[173406-17-2]3-iodobenzoate</strong> (0.87 g, 2.86 mmol), K2CO3 (0.59 g, 4.3 mmol), and (Ph3P)4 Pd (0.17 g, 0.14 mmol) in DME (15 mL) was degassed and flushed with N2 before being brought to reflux for 2 h. Following a standard aqueous/EtOAc work-up, the residue was triturated with 1:10 EtOAc/hexane. The excess boronic acid was removed by filtration, and the filtrate was concentrated to give an oil which was purified by flash chromatography (hexane) to give an oil (0.6 g). This material ('60% pure) was used as such for the next step.
With caesium carbonate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; at 20 - 70℃; for 64h;Inert atmosphere;
A mixture of <strong>[25710-18-3]2,3-dichloropyrido[2,3-b]pyrazine</strong> (Intermediate F step 2) (5 g, 25 mmol), p- tolylboronic acid (4.08 g, 30.0 mmol), tricyclohexylphosphine (1 .682 g, 6.00 mmol), and cesium carbonate (16.29 g, 50.0 mmol) in dry dioxane (60ml) was degassed by bubbling nitrogen through (x3). Tris(dibenzylideneacetone)dipalladium (0) (2.289 g, 2.5 mmol) was added and the reaction mixture was degassed by bubbling nitrogen through (x3). The resulting mixture was stirred at 70 °C for 16 hours and at room temperature for 2 days. The mixture was diluted with water and EtOAc and filtered through Celite.(R).(filter material). The phases were separated and the aqueous extracted with EtOAc The combined organic extracts were washed with brine, dried over MgS04 and concentrated in vacuo. The crude product was purified bychromatography on silica eluting with 0-2percent THF/DCM to give a mixture of the mono and bis arylated products. The materials were re-purified by chromatography on silica eluting with 0-2percent THF/DCM] to afford the title compound;LCMS; Rt 1 .13 mins MS m/z 256/258 [M+H]+ Method 2minl_C_v003
5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-p-tolyl-1H-pyrazole-3-carbonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With bis-triphenylphosphine-palladium(II) chloride; N-iodo-succinimide; sodium hydrogencarbonate; In ethanol; water; at 80℃; for 18h;Inert atmosphere;
General procedure: Phenylpyrazole (0.2 mmol), arylboronic acid (0.4 mmol), NIS (0.2 mmol), [Pd] (10 mol%), NaHCO3 (0.4 mmol) and C2H5OH:H2O (3:1, 10 mL), were added to a Schlenk tube. Then the tube was charged with N2 and the reaction mixture was stirred at 80 C for 18 h. After the completion of the reaction, as monitored by TLC, the mixture was cooled and filtrated. The filtrate was extracted with ethyl acetate and washed with brine. Then the combined organic extracts were dried over Na2SO4, concentrated under vacuum and the resulting residue was purified by silica gel column chromatography to afford the desired products.
With palladium diacetate; potassium carbonate; triphenylphosphine; for 5h;Inert atmosphere; Reflux;
General procedure: To a solution of 5a (2.00 g, 8.58 mmol), Palladium acetate (0.008 g, 0.04 mmol), PPh3 (0.47 g, 1.69 mmol) and p-tolylboronic acid (10 mL) was added 6 mL of 2 M K2CO3. The mixture was refluxed under nitrogen for 5 h, then diluted with ethyl acetate, and washed with water (50 mL * 3) and brine (50 mL * 3).The organic layer was dried over MgSO4. The solvent was removed under reduced pressure.The residue was purified by flash column chromatography with petroleum ether-ethyl acetate (100/1) as eluant.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 75℃; for 4.0h;Inert atmosphere;
General procedure: A 1,4-Dioxane solution (8 mL) of 10 (1.0 mmol), arylboronic acid 2 (1.0 equiv.), K3PO4, and Pd(PPh3)4 (5 molpercent) was heated at 75 C for 4 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).
With potassium phosphate; palladium diacetate; In water; N,N-dimethyl-formamide; at 20℃; for 12h;
General procedure: A DMF/water solution (1:1, 2 mL per 1 mmol of 1) of K3 PO4 (1.5 mmol),Pd(OAc)2 (2 mol %), and arylboronic acid 2a-n (0.9 mmol) was stirred atroom temperature for 8-12 h (tlc control). After completion of the reaction, themixture was extracted with CH2Cl2 and the combined organic layers weredried (Na2SO4), filtered and the filtrate was concentrated in vacuo. The residuewas purified by column chromatography (silica gel, EtOAc/heptane = 1:4).Starting with 1 (216 mg, 1.00 mmol), K3PO4 (165 mg, 1.50 mmol), Pd(OAc)2(2 mol %), arylboronic acid (149 mg, 0.90 mmol), and a solution ofDMF and water (1:1, 5 mL), 3a-3n was isolated
With potassium phosphate; palladium diacetate; In water; N,N-dimethyl-formamide; at 20℃;
General procedure: A DMF/water solution (1:1, 2 mL per 1 mmol of 1) of K3PO4 (1.5 mmol), Pd(OAc)2(2 mol %), and arylboronic acid 2 (2.2 mmol) was stirred at room temperaturefor 8-12 h (tlc control). After completion of the reaction, the mixture wasextracted with CH2Cl2 and the combined organic layers were dried (Na2SO4), filtered and the filtrate was concentrated in vacuo. The residue was purified bycolumn chromatography (silica gel, EtOAc/heptane = 1:4). Starting with 1(216 mg, 1.0 mmol), K3PO4 (345 mg, 2.5 mmol), Pd(OAc)2 (2 mol %), arylboronic acid (334 mg, 2.20 mmol), and solution of DMF andwater (1:1) (2 mL), 4a-f was isolated as a yield.
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 120℃; for 1h;Microwave irradiation;
General procedure: <strong>[290368-00-2]ter<strong>[290368-00-2]t-butyl 3-iodo-1H-indazole-1-carboxylate</strong></strong> (S2, 100 mg, 0.29 mmol) was placed in a microwave vial and dissolved in 1,4-dioxane (11.5 mL). 3-Methoxyphenylboronic acid (88 mg, 0.58 mmol, 2.0 equiv) and tetrakis(triphenylphosphine)palladium (20 mg, 0.017 mmol, 0.06 equiv) were added, and the resulting mixture was sparged thoroughly with nitrogen. An aqueous solution of sodium carbonate (2.0 M, 0.65 mL, 1.3 mmol, 4.5 equiv) was then added. The biphasic mixture was microwaved for 1 hour at a reaction temperature of 120 C. After cooling to room temperature, the reaction was diluted with ethyl acetate (2 mL), and then filtered through a celite pad with additional ethyl acetate. The filtrate was concentrated under reduced pressure to give an oil. The crude material was purified by column chromatography over silica gel (hexanes/ethyl acetate: 100/0 to 30/70) to give the title compound as an oil (58.0 mg, 89%).
With iron(III) oxide; copper(l) iodide; 1,10-Phenanthroline; di-tert-butyl peroxide; lithium tert-butoxide; In toluene; at 110℃; for 12h;Schlenk technique; Sealed tube; Green chemistry;
General procedure: CuI (0.1 mmol), Fe2O3(0.1 mmol), 1,10-phenanthroline(0.1mmol) ,LiOBu-t(1.0 mmol), t-BuOOBu-t(1.0 mmol), benzooxazole(0.5 mmol) and phenylboronic acid(1.0 mmol)were weighed into an oven-dried Schlenk tube which was sealed with a plug. Then toluene(3.0 mL) was added.The reaction mixture was stirred at 110 oC for 12 h. The resulting mixture was then cooled to room temperatureand diluted with ethyl acetate. The organic layer was collected, washed with water and brine, and dried overNa2SO4. After removal of the solvent in vacuo, the residue was purified by silica gel chromatography to give thedesired 2-phenylbenzo[d]oxazole.
With potassium carbonate; In ethanol; water; at 90℃; for 8h;
The sulfadiazine iron-palladium nano-composite particles prepared in Example 1 were used as a catalyst for the catalytic reaction, The reaction conditions are as follows: 1.0 mmol 4- iodophenetole, 1.2 mmol of p-tolylboronic acid and 3.0 mmol of K2CO3, In air atmosphere in H2O / EtOH mixed solvent reaction, The mixed solvent consists of 3mL of water and 4mL of ethanol, the reaction temperature is 90 C, The reaction time was 8h, the product was isolated by column chromatography, The yield is 99%. The reaction equation is as follows:
97%
With potassium carbonate; In ethanol; water; at 50℃; for 4h;
General procedure: A general procedure for the coupling reaction of an aryl halide with arylboronic acid is as follows: aryl halide (1.0 mmol),arylboronic acid (1.2 mmol), K2CO3 (3.0 mmol), ten layers films loaded on quartz slides as catalysts, 4.0 mL H2O and3.0 mL EtOH were added to an flask. The reaction mixturewas heated to a certain temperature in air. After the end of thereaction, the reaction systemwas cooled to roomtemperature,and extracted with ethyl acetate for three times. Then thecombined organic phase was dried over anhydrous Na2SO4.After removal of the solvent, the crude product was purifiedby silica gel columnchromatography using petroleumether toobtain the product with high purity.
With copper diacetate; triethylamine; In dichloromethane; at 0 - 5℃; for 4h;Sonication; Green chemistry;
General procedure: Naphthylboronic acid (0.25 g, 1.5 mmol) was added with 0.094 g of phenol (1.0 mmol) to 15 mL of DCM. Copper(II) acetate (0.36 g, 2.0 mmol) was then added along with triethylamine (0.5g, 5.0 mmol), and the dismembrator horn placed in the reaction vessel. The sonicator was set to 55 watts and the reaction was allowed to proceed for 4 hours (1 minute pulse with a 3 second rest). Post reaction, the product was isolated by column chromatography. Product yields were determined by weight and purity was confirmed by GC/MS and NMR.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 65℃; for 18h;
General procedure: Intermediate 1-4 (5.0 g, 0.009 mol) in 2-methylpyrimidin-4-ylboronic acid (3.0 g, 0.021 mol), Pd (pph3) 4 (0.5 g, 0.0005 mol), potassium carbonate (2.5 g, into a 110 mL THF to 0.018 mol), on reaction with stirring for 18 hours at 65 It turned on. After the reaction cooled to H20: delamination after column purification (n-Hexane: MC) in MC by Compound 130 to 3.8 g (71%) to give Respectively. 3, 3'-dibromobiphenyl (3.1 g, 0.010 mol) to p-tolylboronic acid (1.6 g, 0.012 mol) in the embodiment 1-manufacturing e.g. for inserting and removing (5) the same method used in synthesis of 66-1 as 2.3g intermediate that is (71% yield) is obtained
4-fluoro-4'-methyl-[1,1'-biphenyl]-2-methanol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 70℃;Inert atmosphere;
At room temperature,<strong>[202865-66-5]2-bromo-5-fluorobenzyl alcohol</strong> (410 mg, 2 mmol)P-methylbenzeneboronic acid (299 mg, 2.2 mmol),Anhydrous sodium carbonate (636 mg, 6 mmol) was dissolved in toluene (10 mL)Ethanol (5 mL),Water (5 mL) in a mixed solution.Under nitrogen protection,Tetraphenylphenylphosphine palladium (116 mg, 0.1 mmol) was added,Then stirred at 70 ° C overnight.After the raw material disappears,The reaction solution was cooled to room temperature,The bed was filtered through Celite and washed with ethyl acetate.The filtrate was extracted with ethyl acetate and washed with saturated brine,The organic phases were combined and dried over anhydrous sodium sulfate,Degassed and purified by column chromatography,A yellow liquid 267mg,The yield was 62percent.
With sodium hydroxide; In toluene; at 100℃; for 2h;Schlenk technique;
General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).
With di-tert-butyl dicarbonate; potassium carbonate; magnesium chloride; nickel dichloride; zinc; In tetrahydrofuran; at 20℃; for 20h;
Weigh 1mmol of p-fluorobenzoic acid and 0.5mmol of p-methylbenzeneboronic acid in the reaction flask, With tetrahydrofuran as solvent, 6.5 mg of nickel chloride (0.05 mmol) 98 mg zinc powder (1.5 mmol), 8 mg of bipyridine (0.05 mmol), 138 mg of potassium carbonate (1.0 mmol), 143 mg of magnesium chloride (1.5 mmol), 109 mg of di-tert-butyl dicarbonate (0.5 mmol), The reaction was stirred at room temperature for 20h, to give the desired product isolated 58mg, yield 54percent
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 70℃; for 72h;Inert atmosphere;
Weigh 0.5 mmol (0.324 g)Of tetrakis- (4-bromophenyl) ethylene,2.0 mmol (0.272 g) of 4-methylbenzeneboronic acid and 15 mmol (2.07 g)Potassium carbonate was added to toluene / ethanol / water(20 mL / 10 mL / 5 mL).Vacuum, through nitrogen,After repeating three times,Again the system was added 0.0324g tetrakis triphenylphosphine palladium,Under the protection of N2,Heated at 70 with stirring,Reflux reaction 72h.After the reaction is completed,Cool the solution,Concentrate the solvent, stand still,Precipitation,The precipitate was separated by filtration and recrystallized from toluene solvent,Light green needle-like crystals precipitated in 64percent yield.
4-[4-(p-tolyl)pyrazol-1-yl]piperidine-1-carboxylic acid tert-butyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
139 mg
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In water; N,N-dimethyl-formamide; at 80℃;
To <strong>[877399-50-3]4-(4-bromopyrazol-1-yl)piperidine-1-carboxylic acid tert-butyl ester</strong> (208 mg) were added 4-methylphenylboronic acid (95 mg),N,N-dimethylformamide (3.2 mL),2 M aqueous sodium carbonate solution (946 muL) and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloride. dichloromethane complex (26 mg) and the mixture was stirred at 80°c. After completion of the reaction,saturated brine was added and the mixture was extracted with ethyl acetate. The solvent was evaporated and the obtained residue was purified by column chromatography (hexane:ethyl acetate)to give 4-[4-(p-tolyl)pyrazol-1-yl]piperidine-1-carboxylic acid tert-butyl ester (139 mg).
With potassium phosphate tribasic trihydrate; palladium diacetate; In ethanol; water; toluene; at 70℃; for 12h;
20mmol S15-1, 30.0mmol S15-2, 0.20mmol palladium(II)acetate catalyst and 36mmol trihydrate Potassium phosphate, dissolved in 30mL toluene: ethanol: water in a mixed solvent of water (2:1:2), it was heated at 70 C for 12 h. It was cooled and extracted with dichloromethane (50 mL×3) three times. The organic phase was collected and purified by silica gel column chromatography eluting with petroleum ether:dichloromethane (10:1) to give solid S15-3 8.9 mmol (yield: 44.7%)
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 16h;Inert atmosphere; Reflux;
2,7-dibromo-9,10-phenanthridine (36.6 g, 0.1 mol) was added to a stirred 500 ml three-necked flask.p-Tolueneboronic acid (13.5 g, 0.1 mol), Pd(PPh3)4 (1.2 g, 1 mmol), anhydrous sodium carbonate (21.2 g, 0.2 mol), toluene (100 ml), ethanol (60 ml), water (100 ml).Under nitrogen protection, the reaction mixture was mechanically homogeneous, and the heating was turned on to raise the temperature. The reaction was refluxed for 16 hours, the reaction was completed, the reaction was stopped, and the temperature was lowered.100 ml of ethyl acetate was added to the reaction system, and the solution was separated into water.The phases were washed twice with 100 ml of ethyl acetate.The solvent is then drained and the residue is separated by column chromatography.16.9 g of the intermediate compound M1 was obtained as a white solid, yield 45%.
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