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Chemical Structure| 267221-88-5
Chemical Structure| 267221-88-5
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Product Details of [ 267221-88-5 ]

CAS No. :267221-88-5 MDL No. :MFCD13195770
Formula : C24H26BNO2 Boiling Point : No data available
Linear Structure Formula :(C6H5)2NC6H4BO2C2(CH3)4 InChI Key :VKSWIFGDKIEVFZ-UHFFFAOYSA-N
M.W : 371.28 Pubchem ID :11639307
Synonyms :

Calculated chemistry of [ 267221-88-5 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 28
Num. arom. heavy atoms : 18
Fraction Csp3 : 0.25
Num. rotatable bonds : 4
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 117.6
TPSA : 21.7 ?2

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : Yes
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -4.2 cm/s

Lipophilicity

Log Po/w (iLOGP) : 0.0
Log Po/w (XLOGP3) : 6.15
Log Po/w (WLOGP) : 5.46
Log Po/w (MLOGP) : 4.03
Log Po/w (SILICOS-IT) : 3.66
Consensus Log Po/w : 3.86

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -6.23
Solubility : 0.00022 mg/ml ; 0.000000591 mol/l
Class : Poorly soluble
Log S (Ali) : -6.39
Solubility : 0.000152 mg/ml ; 0.000000409 mol/l
Class : Poorly soluble
Log S (SILICOS-IT) : -8.31
Solubility : 0.00000181 mg/ml ; 0.0000000049 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 3.67

Safety of [ 267221-88-5 ]

Signal Word:Warning Class:
Precautionary Statements:P261-P305+P351+P338 UN#:
Hazard Statements:H302-H315-H319-H335 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 267221-88-5 ]

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

  • Downstream synthetic route of [ 267221-88-5 ]

[ 267221-88-5 ] Synthesis Path-Downstream   1~12

  • 1
  • [ 267221-88-5 ]
  • [ 198964-46-4 ]
  • [ 850153-27-4 ]
YieldReaction ConditionsOperation in experiment
77% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 80℃; for 12h;Inert atmosphere; Under nitrogen protection, add to a 300ml two-neck flask2,7-dibromo-9,9-dioctylfluorene(5.48g, 10mmol),4-(4,4,5,5-tetramethyl-1,3-dioxa-2-boryl)triphenylamine(2.89 g, 10 mmol), potassium carbonate (3.45 g,25mmol), tetrakis(triphenylphosphine)palladium (0.58g, 0.5mmol), 12ml deionized water and 120ml toluene, heating to 80C12 hours.After the reaction was completed, the product was extracted with methylene chloride and washed three times with a saturated aqueous solution of sodium chloride. After removing the solvent of the organic phase, the crude product was eluted with a mixture of petroleum ether:dichloromethane = 8:1 (v/v). Purification by column chromatography gave 5.51 g of a nearly white solid with a yield of 77%.
74.2% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 90℃;Inert atmosphere; As shown in Scheme 1, the triphenylamine 4-borate (0.371 g, 1 mmol) and 9,9-dioctyl-2,7-dibromofluorene (1.192 g, 2 mmol) were dissolved in 15 mL of toluene, into which K2CO3 water solution (2 M, 10 mL) was dropped. Then, tetrakistriphenylphosphine palladium (Pd(PPh3)4) (0.057 g, 0.05 mmol) was added to the above reaction mixture. After refluxing for 4 h under nitrogen protection, the reaction mixture was poured into water and extracted with dichloromethane. The collected organic layer was dried over anhydrous MgSO4 and concentrated under reduced pressure. Finally, the resultant residue was purified by silica gel column chromatography using mixture eluents of ethyl acetate and hexane (1:20, v/v), which afforded M1 as intermediate product (0.3123 g, 74.2%, C47H54BrN: C 79.22, H 7.59, Br 11.22, N 1.97; found: C 79.17, H7.72, Br 11.22, N 1.97). 1H NMR (600 MHz, DMSO) δ 7.86 (d, J = 7.9 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.72 (d, J = 1.3 Hz, 1H), 7.64 (ddd, J = 16.5, 10.7, 8.7 Hz, 4H), 7.51 (dd, J = 8.0, 1.8 Hz, 1H), 7.36-7.29 (m, 4H), 7.10-7.02 (m, 8H), 2.04 (tt, J = 13.3, 8.3 Hz, 4H), 1.25-0.95 (m, 20H), 0.75 (t, J = 7.2 Hz, 6H), 0.49 (s, 4H). 13C NMR (101 MHz, CDCl3) δ 153.15, 151.59, 150.98, 147.68, 147.63, 147.17, 147.00, 139.93, 139.87, 139.73, 139.32, 138.86, 135.63, 135.31, 129.94, 129.27, 128.99, 127.76, 127.27, 126.10, 125.63, 125.50, 124.37, 124.32, 124.28, 124.13, 124.04, 123.93, 122.94, 122.87, 122.79, 122.64, 120.97, 120.86, 120.02, 119.89, 58.36, 55.44, 55.19, 40.47, 40.30, 31.75, 30.02, 29.93, 29.18, 29.15, 23.69, 22.58, 18.38, 14.06.
  • 2
  • [ 61676-62-8 ]
  • [ 267221-88-5 ]
YieldReaction ConditionsOperation in experiment
72.8% Example 11 Synthesis of N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline n-Butyllithium was added dropwise via syringe to a -78 C. (acetone-dry ice cooling bath) solution of 4-bromo-N,N-diphenylaniline (24 g, 0.074 mole) in 175 ml dry THF. Stirring was continued at -78 C. for an hour and then at -50 C. for an hour. The mixture was cooled to -78 C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17.22 g, 0.0925 mole) added via syringe in one portion. The temperature was maintained at -78 C. for three hours. The cooling bath was removed and the reaction left to warm to room temperature while standing for 12 hours. The reaction mixture was poured into saturated ammonium acetate and extracted with ether. The ether layer was dried over magnesium sulfate and concentrated to give a viscous oil. Purification by column chromatography (silica gel eluding with hexane:toluene mixtures of increasing gradient from 100% hexane to 40% hexane) gave N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline as an oil (19.9 g, 72.8% yield), which slowly crystallized to a solid on standing.
  • 3
  • [ 267221-88-5 ]
  • [ 76466-34-7 ]
  • C96H78N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
36% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 20 - 77℃; for 5.5h; SYNTHESIS EXAMPLE 2Synthesis of Exemplified Compound No. 7 1.0 g (1.59 mmol) of the tetrabromo intermediate (3), 4.7 g (12.7 mmol) of pinacolborane (5), 200 ml of toluene, and 70 ml of ethanol were loaded into a 500-ml three-necked flask. An aqueous solution of 12.8 g of sodium carbonate in 64 ml of water was dropped to the mixture while the mixture was stirred in a nitrogen atmosphere at room temperature. Next, 0.37 g (0.32 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to the mixture. After the mixture had been stirred at room temperature for 30 minutes, the temperature of the mixture was increased to 77 C., and the mixture was stirred for 5 hours. After the reaction, an organic layer was extracted with chloroform, dried with anhydrous sodium sulfate, and purified with a silica gel column (mixed developing solvent of hexane and toluene), whereby 0.74 g of Exemplified Compound No. 7 (white crystal) was obtained (36% yield).
  • 4
  • [ 61676-62-8 ]
  • [ 36809-26-4 ]
  • [ 267221-88-5 ]
YieldReaction ConditionsOperation in experiment
72% Was dissolved I-1 10 g (30.84 mmol) in a 170 ml of tetrahydrofuran was stirred at -78 . After the addition of 1.6M n-BuLi 20.24ml (32.39 mmol) slowly, it stirred for 30 minutes at -78 . Isopropoxy -4,4,5,5- tetramethyl- [1,3,2] dioxa-beam as is after the addition of 7.55 ml (37.01 mmol) slowly, and stirred for 6 hours at -78 . After the reaction was added to 100 ml of distilled water and extracted with ethyl acetate. The solvent was evaporated and then the filter was dried with magnesium sulfate. After column chromatography Intermediate I-2 (N, N- diphenyl-4- (4,4,5,5-dioxa-beam is a methyl -1,3,2--2-yl) aniline) via the to give the 8.24 g (72% yield).
70% 4-bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF under argon atmosphere at -78 & lt; 0 & gt; CWas added dropwise 1.6 ml of 1.6 mol of L-1 n-butyllithium, reacted for 2 hours, and then 2-isopropoxy-4,4,5,5-tetrakis Methyl-1,3,2-dioxaborolane, and the reaction was continued at -78 C for 1 hour, and the temperature was gradually raised to room temperature for 24 hours. will The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate. The solution was concentrated to give a crude product as a pale yellow viscous material which was purified by silica gel column chromatography (eluent selection of petroleum ether / ethyl acetate =20/1, v / v), the product was left in the refrigerator for a long time to give a white solid in 70% yield.
70% Under an argon atmosphere,4-bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF and 1.6 mL of L-1 of n-butyllithium was gradually added dropwise at -78 C for 2 hours,And then rapidly adding 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane,The reaction was continued at -78 C for 1 hour and slowly warmed to room temperature for 24 hours.The reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was completely washed with brine,Add anhydrous magnesium sulfate dry. After the solution was concentrated, a crude product was obtained as a pale yellow viscous,Purification by silica gel column chromatography (eluent selection petroleum ether / ethyl acetate = 20/1, v / v)The product was left in a refrigerator for a long time to give a white solid in 70% yield.
70% Under an argon atmosphere,4-bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF,1.6 mL of L-1 of n-butyllithium was gradually added dropwise at -78 C,Reaction for 2 hours,And then rapidly adding 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane,The reaction was continued at -78 & lt; 0 & gt; C for 1 hour,Slowly warm to room temperature for 24 hours. The reaction mixture was poured into water,Extracted with ethyl acetate, and the organic layer was completely washed with brine,Add anhydrous magnesium sulfate dry.After the solution was concentrated, a crude product was obtained as a pale yellow viscous,Purification by silica gel column chromatography (eluent selection petroleum ether / ethyl acetate = 20/1, v / v)The product was left in a refrigerator for a long time to give a white solid in 70% yield.
70% 4-Bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF under argon atmosphere at -78 & lt; 0 & gt; CWas added dropwise 1.6 mL of 1.6 mol of L-1 n-butyllithium, reacted for 2 hours, and then 2-isopropoxy-4,4,5,5-tetrakisMethyl-1,3,2-dioxaborolane, the reaction was continued at -78 C for 1 hour, and the temperature was gradually raised to room temperature for 24 hours.The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfate.The solution was concentrated to give a crude product as a pale yellow viscous material which was purified by silica gel column chromatography (eluent selection of petroleum ether / ethyl acetate =20/1, v / v) and the product was placed in a refrigerator to give a white solid in 70% yield.
70% Under an argon atmosphere,A solution of 4-bromotriphenylamine (5 g, 15.52 mmol)Was dissolved in 180 mL of purified THF,1.6 mL of L-1 of n-butyllithium was gradually added dropwise at -78 C,Reaction for 2 hours,Then, 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added rapidly,The reaction was continued at -78 1 hourSlowly warm to room temperature for 24 hours.The reaction mixture was poured into water,Extracted with ethyl acetate,After the organic layer was completely washed with brine,Add anhydrous magnesium sulfate dry.After the solution was concentrated,Get light yellow viscous thick,Purification by silica gel column chromatography (eluent selection of petroleum ether / ethyl acetate = 20/1, v / v)The product stored in a refrigerator for a long time to give a white solid,Yield 70%.
70% In the argon atmosphere, will be 4 - bromo-aniline (5 g, 15.52 mmol) is dissolved in 180 ml of THF in refining, in -78 C gradually dropping 1.6 μM L-1N-butyllithium of 28 ml, reaction 2 hours, then quickly add 2 - isopropoxy - 4, 4, 5, 5 - tetramethyl - 1, 3, 2 - dioxa borane 25 ml, in -78 C continues reaction under 1 hour, slow heating to room temperature, the reaction 24 hours; in the reaction mixture is poured into water, extracted with ethyl acetate, the organic layer using salt water completely after washing, add anhydrous magnesium sulfate drying; after concentrating the solution, to obtain yellowish viscous shape thick, purification with silica gel column chromatography (elution agent selected petroleum ether/ethyl acetate=20/1, v/v), the product is placed in the refrigerator, to obtain white solid, yield 70%.
70% Under an argon atmosphere 4-bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF, and 28 mL of 1.6 mol I / 1 n-butyllithium was gradually added dropwise at -78 C. and reacted for 2 hours. Then, 2- Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborne 25mL, the reaction was continued at -78 C for 1 hour, slowly warmed to room temperature for 24 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and then dried over anhydrous magnesium sulfate.The solution was concentrated to give a pale yellow viscous crude product, which was purified by silica gel column chromatography (eluent petroleum ether / ethyl acetate = 20/1, v / v). The product was left in the refrigerator for a long time to give a white solid in a yield of 70%.
70% Under an argon atmosphere,willBromo-triphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF,28 mL of 1.6 mol L-1 n-butyllithium was gradually added dropwise at -78 C, and reacted for 2 hours,Then 25 mL of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborne was added rapidly,The reaction was continued at -78 C for 1 hour, slowly warmed to room temperature and allowed to react for 24 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed thoroughly with brine and dried over anhydrous magnesium sulfateThe solution was concentrated to give a pale yellow viscous crude which was purified by silica gel column chromatography (eluent petroleum ether / ethyl acetate = 20/1, v / v). The product was placed in a freezer to give a white solid, Yield 70%.
70% Under an argon atmosphere, 4-bromotriphenylamine (5 g, 15.52 mmol) was dissolved in 180 mL of purified THF, and 1.6 mol of I/1 n-butyllithium 28 mL was gradually added dropwise at -78 C. for 2 hours, and then quickly added 2- Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolidine 25mL, at -78 C to continue the reaction for 1 hour, slowly warming to room temperature, the reaction for 24 hours; The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was completely washed with brine and dried over anhydrous magnesium sulfate. After the solution was concentrated, a pale yellow viscous crude product was obtained and purified by silica gel column chromatography (eluting The agent was selected from petroleum ether/ethyl acetate = 20/1, v/v) and the product was placed in a refrigerator to obtain a white solid, yield 70%.
49% Put the dried M1 (10g, 30.8mmol) and 50ml of tetrahydrofuran (tetrahydrofuran was previously refluxed with sodium to remove water) in a 250ml round bottom flask. After degassing in the frozen state of liquid nitrogen, the flask was placed in a low-temperature reactor at -78 C and stirred for half an hour. Next, n-BuLi (n-BuLi, 37 mmol, 15.4 ml, 1.2 equivalents) was slowly dropped into the flask under the protection of nitrogen. After stirring for one hour, isopropanol pinacol borate (37 mmol, 1.2 equivalents) ) Slowly dropped into the flask, and after stirring for half an hour, the flask was removed from the low-temperature reactor and left to stir at room temperature for 24 hours. After the reaction was completed, the reaction solution was washed three times with deionized water and extracted with dichloromethane. The organic solution was dried with anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the solvent was evaporated to dryness using a rotary evaporator. Then, it is purified by silica gel column chromatography to obtain an oily product. The developing agent is a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1: 6. The oily product was recrystallized from absolute ethanol to obtain a white solid product (M2) with a yield of 49%.
45% EXAMPLE 16 2-(4-Diphenylaminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane To a flame-dried 3-neck, round-bottomed 500 mL flask equipped with mechanical stirring and an addition funnel was added 4-bromotriphenylamine (12.5 g, 39.5 mmol) and THF (250 mL) by cannula. The solution was cooled to -78 C. and 1.6 M n-BuLi in hexane (26.5 mL, 42.4 mmol) was added by addition funnel over 15 min. After stirring for 30 min, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.8 mL, 48.2 mmol) was added dropwise, and the reaction mixture was allowed to warm to room temperature overnight. Toluene and water were added, and the organic phase was further washed with water, dried with MgSO4, and concentrated. The crude product was purified by column chromatography eluting with hexane, 2/1 hexane/CH2Cl2, and finally 1/1 hexane/CH2Cl2 to give 6.4 g (45%) white crystals. 1H NMR (400 MHz, CDCl3) δ: 7.66 (m, 2H), 7.26 (m, 4H), 7.10 (m, 4H), 7.04 (m, 4H); GC-MS (m/z): 371 (M+), >97% purity. Anal. Calcd. for C24H26BNO2: C, 77.64%; H, 7.06%; B, 2.91%; N, 3.77%. Found: C, 77.78%; H, 7.21%; B, 2.70%; N, 3.53%.
4-bromotriphenylamine (1.0 g, 3.08 mmol) dissolved in 40 mL of THF is then cooled to -78 0 C and 1.36 mL (3.4 mmol) of n-butyllithium (2.5 M n-hexane) are added dropwise thereto. After the mixture was stirred at -78 C for 1 hour, 2-Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (0.688 g, 3.7 mmol) is slowly added at -78 0 C and the reaction is slowly warmed to room temperature and stirred overnight. The mixture is poured into water and the product is extracted with chloroform. The organic phase is dried with Na2S04, filtered and the solvent is evaporated completely. N,N- diphenyl -4-(4, 4,5,5- tetramethyl -1,3,2- dioxaborolan -2-il) aniline (5) is obtained as pink solid

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  • 5
  • [ 36809-26-4 ]
  • [ 73183-34-3 ]
  • [ 267221-88-5 ]
YieldReaction ConditionsOperation in experiment
95% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 85℃; for 16h; 2.2.9 3,6-bis(5-(4-(Diphenylamino)phenyl)furan-2-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (10) Compound 10 was synthesized by following the procedure used for the synthesis of compound 9. Herein, 6 (0.800 g, 1.23 mmol), 8 (1.01 g, 2.71 mmol), bis(dibenzylideneacetone)palladium (0) (Pd2(dba)3) (0.023 mg, 0.0245 mmol), tri-o-tolylphosphine (P(o-tol)3) (0.030 g, 0.098 mmol), anhydrous K2CO3 (1.60 g, 11.68 mmol), 2 drops of aliquat 336 were used, (Yield = 62.5%). 1H NMR (400 MHz, CDCl3) δppm: 8.37 (s, 2 H), 7.55-7.57 (d, 4 H), 7.29-7.24 (t, 8 H), 7.12-7.05 (m, 16 H), 4.17 (t, 4 H), 1.76 (m, 4H), 1.57-1.18 (m, 20H), 0.78 (t, 6H). 13C NMR (400 MHz, CDCl3) δppm: 160.81, 157.04, 148.55, 147.02, 143.50, 132.18, 129.44, 125.44, 125.09, 123.76, 122.69, 122.50, 107.97, 42.56, 31.72, 30.35, 29.43, 29.22, 27.13, 22.56, 14.04. ESI-HRMS calcd for C66H66N4O4 979.28, found 979.35.
89% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 6h; 3.24 g (10.0 mmol) of 4-bromotriphenylamine, 2.54 g (10.0 mmol) of bis(pinacolato)diborone, 0.36 g(0.5 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloro palladium (II) (hereinafter, PdCl2(dppf)2), and 2.94 g (30.0 mmol) of KOAc were dissolved in 40 mL of dimethylsulfoxide (DMSO) to obtain a solution, which was then stirred at about 80C for about 6 hours. The reaction solution was cooled to room temperature, followed by three times of extraction with 50 mL of water and 50 mL of diethylether. The organic phase was collected, and was dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 2.57 g of Intermediate I-5 (Yield: 89 %). This compound was identified using LC-MS and NMR C24H26BNO2 : M+ 371.2 1H NMR (CDCl3, 400MHz) δ (ppm) 7.67-7.63 (m, 2H), 7.30-7.21 (m, 4H), 7.14-7.06 (m, 4H), 7.05-7.00 (m, 4H), 1.32 (s, 12H)
89% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 6h; Synthesis of Intermediate I-4 3.24 g (10.0 mmol) of 4-bromotriphenylamine, 2.54 g (10.0 mmol) of bis(pinacolato)diborone, 0.36 g (0.5 mmol) of 1,1'-bis(diphenylphosphino)ferrocene]dichloro palladium (II) (PdCl2(dppf)2), and 2.94 g (30.0 mmol) of KOAc were dissolved in 40 ml of dimethyl sulfoxide (DMSO), and the mixture stirred at 80C for 6 hours. The mixture was cooled to room temperature and subjected to extraction three times with 50 ml of water and 50 ml of diethyl ether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 2.57 g of Intermediate I-4 (Yield: 89 %) The produced compound was identified using HR-MS. C24H26BNO2 Calc.: 371.2057; Measured: 371.2051
89% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90℃; Said M 1-I-1 obtained in the synthesis (112.78g, 347.9mmol) senses a rotation velocity of the disk to a DMF to in round bottom flask , Bis (pinacolato) diboron (97.17g, 382.6mmol), Pd (dppf) Cl 2 (8.52g, 10.4mmol), KOAc (102.42g, 1043.6mmol) added 90 C stirring section. When reaction is completed by etching are removed and then the DMF via fractional distillation CH 2 Cl 2 extracted and water. Organic layer MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 114.95g (yield: 89%)is obtained.
89% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 80℃; for 6h; 4-bromo-triphenyl amine 3.24g (10.0mmol), Bis (pinacolato) diborone 2.54g (10.0mmol), PdCl2 (dppf) 2 0.36g (0.5mmol), and KOAc 2.94g (30.0mmol) dissolved in 40mL of DMSO after stirring at 80C for 6 hours. After cooling the reaction solution to room temperature and extracted three times with 50mL of water and 50mL of diethyl ether. Dry the organic layer obtained therefrom by separating the magnesium sulfate, and the residue obtained by evaporating the solvent was subjected to silica gel column chromatography to give the purified intermediate I-8 2.57g (89% yield). The resulting compound was confirmed by NMR and HR-MS.
89% With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate; In 1,4-dioxane; for 21h;Inert atmosphere; Reflux; Under an argon atmosphere, palladium chloride (80 mg, 0.45 mmol) and 1,1'-bis(diphenylphosphino)ferrocene (249 mg, 0.45 mmol) were dissolved in 1,4-dioxane (40 mL) After stirring, bromotriphenylamine (4.86 g, 15.0 mmol), bispinacolatodiboron (4.19 g, 16.5 mmol), potassium acetate (4.42 g, 45.0 mmol) and dioxane (90 mL) were added to a solution of Was added sequentially. The reaction mixture was stirred under heating reflux for 21 hours. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Sodium sulfate was added to the organic layer, which was separated by filtration, and the solvent was distilled off to obtain a crude product. This was purified by silica gel column chromatography (developing solvent: hexane / chloroform = 2/1 to 1/1) to obtain the objective 4-(diphenylamino)phenylboronic acid pinacol ester as a white solid (4.96 g , 89%).
89.4% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 85℃; for 12h;Inert atmosphere; 4-Bromotriphenylamine (5.01 g, 15.43 mmol), bis(pinacolato)diboron (9.81 g, 38.58 mmol), PdCl2(dppf) (1.13 g, 1.54 mmol), KOAc (6.05 g, 61.72 mmol) in a 100 ml three-necked flask, the air in the reaction tube was replaced with N2, and 50 ml of 1,4-dioxane was injected as a solvent under N2, and reacted at 85 C for 12 h. After completion of the reaction, the mixture was cooled to room temperature. After cooling, the reaction mixture was evaporated to dryness, purification by silica gel column chromatography (V ( petroleum ether) / V (dichloromethane) = 100/1) to obtain white solid M-1 (5.1 g, 89.4%).
88.1% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 80℃; for 5h;Inert atmosphere; In a 250 mL three-necked flask, nitrogen was bubbled with 0.02 mol of 4-bromotriphenylamine in 100 ml of tetrahydrofuran (THF) and 0.024 mol of bis (pinacolato) diboron, 0.0002 mol (Diphenylphosphino) ferrocene) dichloropalladium (II) and 0.05 mol of potassium acetate were added, and the mixture was stirred, and the mixed solution of the above reaction was heated under reflux at reflux temperature for 5 hours. After the completion of the reaction , Cooled and added with 100 ml of water, and the mixture was filtered and dried in a vacuum oven. The obtained residue was purified by silica gel column to obtain triphenylamine-4-boronic acid pinacol ester; HPLC purity was 99.7% and the yield was 88.1%.
87% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90℃; Wherein M 2-I-1 (63.01 g, 194.3 mmol) to a round bottom flask was charged with DMF (970 ml) to dissolve later, Bis (pinacolato) diboron (54.29 g, 213.8 mmol), PdCl2 (dppf) (4.76 g, 5.8 mmol), was added KOAc (57.22 g, 583 mmol) and the resulting mixture was stirred at 90 C. After completion of reaction by distillation to remove DMF and CH2Cl2. And extracted with water. The organic layer was dried over MgSO4 and concentrated and the resulting product was compound silicagel column and recrystallization 62.78 g (yield:87% was obtained).
86% With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate; palladium diacetate; acetic acid; In 1,4-dioxane; at 90℃; for 15h;Inert atmosphere; Reflux; To a two-necked flask was added Compound 3 (4.86 g, 15 mmol), pinacolate (4.95 g, 19.5 mmol),Palladium acetate (0.1 g, 0.45 mmol), dppf (0.5 g, 0.9 mmol) and potassium acetate (4.42 g, 45 mmol)Dioxane (50 ml) was added, and the mixture was refluxed at 90 C for 15 h. After the reaction, deionized water (3x50ml) was extracted with DCM (100ml). The organic phase was dried over anhydrous magnesium sulphate and evaporated to DCM. The product 5 was obtained by column chromatography.
80% To a three-necked flask adding 1,4-dioxane solution of 4-bromotriphenyl amine (5 g, 15.42 mmol), bis(pinacolato)diboron (4.7 g,18.5 mmol) and CH3COOK (4.54 g, 46.62 mmol), The solution waspurged with argon for 30 min, and then Pd(dppf)Cl2 (0.38 g,0.465 mmol) was added. The reaction was stirred at 85 C overnight.The reaction followed by TLC until reaction completion, then let the reaction to cool down and the reaction quenched by adding (50 ml) ofwater then extracted by ethyl acetate (3×30 ml) The combined organiclayers were dried over anhydrous Mg2SO4, and the solvent wasremoved under vacuum. The crude product was purified by column chromatography on silica with hexane/ethyl acetate mixture (6: 1). The compound crystalized from anhydrous ethanol and give the pure white powder. Yield (80%), melting point (m.p) 93 C. FT-IR (cm-1):2976-2990 (CH for CH3), 1591 (C = C aromatic), 1278 (C--N aromaticamine).
Ca. 75% With bis-triphenylphosphine-palladium(II) chloride; potassium acetate; In N,N-dimethyl-formamide; for 6h;Inert atmosphere; Reflux; Compound 2was synthesized according to the modified reportedprocedures.25 4-Bromo triphenylamine, 1 (0.32 g,1 mmol), bis(pinacolato)diborane (0.38 g, 1.5 mmol),KOAc (0.4 g, 4 mmol) and Pd(PPh3)2Cl2 (35mg,0.05 mmol) were dissolved in minimum amount ofdegassed N,N-dimethyl formamide (DMF) in a 100mLround bottom (RB) flask. Subsequently, the reactionmixture was subjected to reflux for 6 h under nitrogenatmosphere and the reaction was monitored by TLC.After completion of reaction, the solvent was evaporatedunder vacuum and crude compound was extractedwith dichloromethane and concentrated using rotaryevaporator. The crude compound was purified by columnchromatography by employing silica gel as stationaryphase and ethyl acetete:hexane (2:98) as eluting solvent.Yield ～75%.
75% With tris-(dibenzylideneacetone)dipalladium(0); sodium acetate; tri tert-butylphosphoniumtetrafluoroborate; In 1,4-dioxane; for 12h;Inert atmosphere; Reflux; General procedure: Under the protection of argon, compound 4 (1 eq.), bis(pinacolate)diboron (1.25 eq.), NaOAc (3.12 eq.) were dissolved in dry argonpurged1,4-dioxane. Then, Pd2dba3 (0.005 eq.) and [(t-Bu)3PH]BF4(0.02 eq.) were added to the system and stirring at reflux for 12 h. Thereaction mixture was then cooled down to room temperature and extractedwith CH2Cl2, the organic layer was dried over anhydrousNa2SO4, and the solvent was removed by rotary evaporator. The residuemixture was purified by column chromatography on silica gel usinghexane/CH2Cl2 (1:1) as the eluent to obtain the derivatives 5a and 5b.2.5.1. (5a)Yield 75%, 93 mg. 1H NMR (400 MHz, CHCl3-d) 4/ppm=4 7.67 (d,J=8.5 Hz, 2H), 7.26 (t, J=8.0 Hz, 4H), 7.11 (d, J=7.5 Hz, 4H), 7.05(t, J=8.5 Hz, 4H), 1.34 (s, 12H). 13C NMR (100 MHz, CHCl3-d) 4/ppm=150.6, 147.4, 136.4, 135.9, 129.3, 125.0, 123.4, 121.8, 83.6,24.9. MS (EI): m/z calcd for [C24H26BNO2]+: 371.29; found: 371.40. Anal. Calcd for C24H26BNO2: C, 77.64; H, 7.06; N, 3.77%. Found: C,77.59; H, 7.02; N, 3.75%.
63% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; at 85℃; for 15h;Inert atmosphere; Under inert atmosphere, a degassed solution of 1(3.000 g, 9.250 mmol), bis(pinacolato)diboron (3.054 g,12.255 mmol), KOAc (3.018 g, 32.225 mmol),and Pd(dppf)2Cl2 (0.338 g, 0.05 mmol) in drydimethoxyethane (30 mL) was heated under reflux conditionsfor 15 h. After this period, the mixture wascooled to room temperature, filtered, and diluted withCH2Cl2 (50 mL). The organic solution was washed withH2O (2×30 mL) and brine, then dried (with anhydrousMgSO4 and evaporated. The residue was separated bycolumn chromatography using hexane/CH2Cl2 (9/1 v/v)to give compound 2 as a white solid product (2.170 g,63%). 1H NMR (300 MHz, CDCl3: 7.74-7.59 (d, 2H),7.19-7.08 (d, 4H), 7.07-6.90 (t, 4H), 1.48-1.16 (t, 12H).
63% With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate; In 1,2-dimethoxyethane; for 15h;Heating; Substance (1) (3.000 g, 9.250 mmol), bis (pinacolao) diboron) (3.054 g, 12.255 mmol), KOAc (3.018 g,32.225 mmol) and Pd (dppf) 2 Cl 2 (0.338 g, 0.05 mmol) are heated in dried Dimethoxyehane (30 mL) for 15 h.The product is then cooled to room temperature, filtered and diluted with dichloromethane (CH 2 Cl 2, 50 mL). The prepared solution is washed with water and brine, dried over anhydrous magnesium sulfate (MgSO 4) and evaporated.The final product was then separated using hexane / dichlorometal (hexane / Ch2Cl2 (9/1 v / v) column chromatography) to give a white solid (2.170 g, yield = 63%).
60% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 16h;Inert atmosphere; Reflux; A mixture of [1,1′ -Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.20 g, 0.27 mmol), bis(pinacolato)diboron (2.44 g, 9.60 mmol), 4-bromo-N,N-diphenylamine (2.56g, 8.00 mmol), KOAc (2.16 g, 22.00 mmol) and dehydrated 1,4-dioxane(100 mL) in a round bottom flask was refluxed under argon atmospherefor 16 h. The reaction mixtures were concentrated, extracted bydichloromethane, and purified by column chromatography (petroleumether/dichloromethane = 10/4, v/v) to afford the white solids with ayield of 60% (1.78 g). 1H NMR (600 MHz, CDCl3) 7.66 (d, J = 8.4 Hz,2H), 7.26-7.24 (m, 4H), 7.10 (d, J = 7.8 Hz, 4H), 7.05-7.02 (m, 4H),1.33 (s, 12H).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 85℃; for 24h;Inert atmosphere; (1) Add in a 250 ml three-neck round bottom reaction flask under a nitrogen atmosphere9.71 g of 4-bromotriphenylamine and 15.6 g of pinacol borate, followed by 240 ml of dioxane,24 g of potassium acetate was agitated for 30 minutes.Finally, 700 mg of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride was added, and after aeration for 30 minutes, it was heated to 85 C and refluxed for 24 hours.After the reaction is stopped and the reaction is stopped, the solvent of the reaction system is removed by rotary evaporation.The intermediate product N,N-biphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline was obtained.
9.2 g With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dichloromethane; dimethyl sulfoxide; at 90℃; for 8h;Inert atmosphere; In a reaction vessel under a nitrogen atmosphere, 10.0 g of a compound represented by the formula (L1-1-27-3), 8.6 g of bis (pinacolato) diborone, 4.5 g of potassium acetate,100 mL of dimethyl sulfoxide and 0.5 g of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct were added, and the mixture was heated with stirring at 90 C for 8 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) gave 9.2 g of a compound represented by the formula (L1-1-27-4).

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  • 6
  • [ 267221-88-5 ]
  • [ 171408-84-7 ]
  • [ 1245645-82-2 ]
  • 7
  • [ 267221-88-5 ]
  • [ 15155-41-6 ]
  • [ 830325-93-4 ]
YieldReaction ConditionsOperation in experiment
62% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 88℃; for 13h;Reflux; Inert atmosphere; C6H2Br2N2S (1.266 g, 4.308 mmol), C24H26BNO2, (400 mg, 1.077 mmol), Pd(PPh3)4,A mixture of K2CO3 (12.5 ml), CH3CH2OH (12.5 ml) in toluene (25.0 ml) was stirred and heated.It was refluxed at 88 C for 13 hours under a nitrogen atmosphere.The crude product was extracted three times with dichloromethane and water.It was dried over anhydrous Na 2 SO 4 .then,Using petroleum ether and dichloromethane (4:1) as the eluent,The crude product is purified by silica gel column chromatography to give the title compound.It was a pale yellow solid (yield: 62%).
  • 8
  • [ 267221-88-5 ]
  • [ 1373131-51-1 ]
  • [ 1373131-52-2 ]
YieldReaction ConditionsOperation in experiment
72% With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 70℃; for 5h; 2.23 g (5.0 mmol) of Intermediate I-4, 1.86 g (5.0 mmol) of Intermediate I-5, 0.29 g (0.25 mmol) of Pd(PPh3)4, and 2.07 g (15.0 mmol) of K2CO3 were dissolved in 30 mL of a mixed solution THF/H2O (2:1) to obtain a solution, which was then stirred at about 70C for about 5 hours. The reaction solution was cooled to room temperature, followed by three times of extraction with 50 mL of water and 50 mL of diethylether. The organic phase was collected, and was dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 2.11 g of Compound 3 (Yield: 72 %). This compound was identified using LC-MS and NMR. C46H30N2 : M+ 610.2 1H NMR (CDCl3, 400MHz) δ (ppm) 9.26-9.22 (d, 1H), 8.92-8.90 (dd, 1H), 8.43-8.41 (d, 1H), 8.34-8.31(d, 1H), 8.27-8.24 (d, 1H), 8.10 (s, 1H), 8.03-7.98 (dd, 2H), 7.74-7.72 (m, 4H), 7.59-7.52 (m, 6H), 7.35-7.22 (m, 10), 7.10-7.05 (dt, 2H)
  • 9
  • [ 73183-34-3 ]
  • [ 267221-88-5 ]
YieldReaction ConditionsOperation in experiment
96% With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In N,N-dimethyl-formamide; at 80℃; for 30h;Inert atmosphere; 1.0 g of 4-bromotriphenylamine, 0.86 g of bis(pinacol)diborane, 1.8 g of potassium acetate, and 100 mL of N,N-dimethylformamide (abbreviation: DMF) in a 200 mL three-neck flask. The air in the flask was replaced by nitrogen. Then, 150 mg of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (abbreviation: PdCl2(dppf)) was added to this mixture, and the mixture was heated and stirred under a nitrogen stream at 80 C. for 30 hours to cause a reaction. After the reaction, about 100 mL of water was added to the solution and the mixture was stirred for 30 minutes. After the stirring, this suspension was separated, and an organic layer was fractionated. The resulting aqueous layer was subjected to extraction with ethyl acetate and combined with the previously obtained organic layer, and washing was performed using water and saturated saline in this order. After the washing, anhydrate magnesium sulfate was added to the solution for drying. After the drying, the solution was gravity filtered and the resulting filtrate was concentrated to obtain a brown oily substance. This brown oily substance was dissolved in hexane and the precipitated solid was removed by filtration, thereby obtaining a filtrate. This filtrate was concentrated to obtain a pale yellow oily substance (96% yield). The synthesis scheme of Step 1 is shown by (a-2).
  • 10
  • [ 267221-88-5 ]
  • [ 38557-72-1 ]
  • 3,5-dimethyl-2-(4-diphenylaminophenyl)pyrazine [ No CAS ]
YieldReaction ConditionsOperation in experiment
30% With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In water; acetonitrile; for 0.333333h;Inert atmosphere; Microwave irradiation; 0.36 g of <strong>[38557-72-1]2-chloro-3,5-dimethylpyrazine</strong>, 0.92 g of 4,4,5,5-tetramethyl-2-(4-diphenylaminophenyl)-1,3,2-dioxaborolane obtained in Step 1, 0.26 g of sodium carbonate, 0.011 g of bis(triphenylphosphine)palladium(II) dichloride (abbreviation: Pd(PPh3)2Cl2), 10 mL of water, and 10 mL of acetonitrile in a recovery flask equipped with a reflux pipe. The air in the flask was replaced by argon. This reaction container was heated by microwave irradiation (2.45 GHz, 100 W) for 20 minutes. After that, the reaction container was cooled to 50 C. or lower, water was added to the reaction solution, and the organic layer was subjected to extraction with dichloromethane. The obtained organic layer was washed with water and dried with magnesium sulfate. After the drying, the solution was filtered. The solvent of this solution was distilled, and the obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate as a developing solvent, thereby obtaining the objective pyrazine derivative Hdmdpappr (white powder, 30% yield). Note that the microwave irradiation was performed using a microwave synthesis system (Discover, produced by CEM Corporation). The synthesis scheme of Step 2 is shown by (b-2).
  • 11
  • [ 267221-88-5 ]
  • [ 1416070-72-8 ]
  • [ 1416070-74-0 ]
YieldReaction ConditionsOperation in experiment
75% With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 70℃; for 5h; Synthesis of Compound 101 1.66 g (5.0 mmol) of Intermediate I-3, 1.86 g (5.0 mmol) of Intermediate I-4, 0.29 g (0.25 mmol) of Pd(PPh3)4, and 2.07 g (15.0 mmol) of K2CO3 were dissolved in 30 ml of a THF/H2O (2/1) solution, and the mixture was stirred at 70C for 5 hours. The mixture was cooled to room temperature and subjected to extraction three times with 50 ml of water and 50 ml of diethyl ether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 1.86 g of Compound 101 (Yield: 75 %). The produced compound was identified using HR-MS and NMR. C37H24N2 Calc.: 496.1939; Measured [M+1] 497.1922 1H NMR (CDCl3, 400MHz) δ (ppm) 8.92-8.90 (m, 1H), 8.70-8.67 (m, 1H), 8.29-8.22 (m, 3H), 8.17-8.14 (m, 2H), 8.03 (d, 1H), 7.68 (d, 1H), 7.53-7.48 (m, 2H), 7.45-7.42 (m, 1H), 7.08-7.04 (m, 4H), 6.98-6.93 (m, 2H), 6.67-6.63 (m, 2H), 6.17-6.13 (m, 4H).
  • 12
  • [ 267221-88-5 ]
  • 5-(3,4',5'-tribromo-2,2'-bithiophene)carbaldehyde [ No CAS ]
  • 5-(3,4',5'-tris(4-(diphenylamino)phenyl)-2,2'-bithiophene)carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; water; toluene; at 90℃; for 48h;Schlenk technique; Inert atmosphere; General procedure: In a Schlenk tube, borate ester (3-5) (4.5 equiv.), aldehyde 2 (1.0 equiv.), Pd(PPh3)4 (0.08 equiv.) and Cs2CO3 (8.0 equiv.) were dissolved in a degassed mixed solvent of toluene/EtOH/H2O. The mixture was heated at 90 C under an argon atmosphere for 2 days. After then, the organic phase was separated, dried over anhydrous Na2SO4 and filtered off. The filtrate was evaporated to dryness and purified by silica gel column chromatography with EtOAc/petroleum ether (1:6) as eluent to afford target aldehydes (6-8).
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