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[ CAS No. 78600-33-6 ] {[proInfo.proName]}

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Chemical Structure| 78600-33-6
Chemical Structure| 78600-33-6
Structure of 78600-33-6 * Storage: {[proInfo.prStorage]}
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Product Details of [ 78600-33-6 ]

CAS No. :78600-33-6 MDL No. :MFCD06798123
Formula : C18H14BrN Boiling Point : -
Linear Structure Formula :- InChI Key :YDXLVFKTOSKBKT-UHFFFAOYSA-N
M.W : 324.21 Pubchem ID :16217851
Synonyms :

Calculated chemistry of [ 78600-33-6 ]

Physicochemical Properties

Num. heavy atoms : 20
Num. arom. heavy atoms : 18
Fraction Csp3 : 0.0
Num. rotatable bonds : 3
Num. H-bond acceptors : 0.0
Num. H-bond donors : 0.0
Molar Refractivity : 88.83
TPSA : 3.24 Ų

Pharmacokinetics

GI absorption : Low
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : Yes
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -4.12 cm/s

Lipophilicity

Log Po/w (iLOGP) : 3.57
Log Po/w (XLOGP3) : 5.85
Log Po/w (WLOGP) : 5.92
Log Po/w (MLOGP) : 5.51
Log Po/w (SILICOS-IT) : 4.41
Consensus Log Po/w : 5.05

Druglikeness

Lipinski : 1.0
Ghose : None
Veber : 0.0
Egan : 1.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -6.0
Solubility : 0.000322 mg/ml ; 0.000000992 mol/l
Class : Poorly soluble
Log S (Ali) : -5.69
Solubility : 0.000662 mg/ml ; 0.00000204 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -7.6
Solubility : 0.00000822 mg/ml ; 0.0000000254 mol/l
Class : Poorly soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.6

Safety of [ 78600-33-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H317-H319-H335-H413 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 78600-33-6 ]

* 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 [ 78600-33-6 ]

[ 78600-33-6 ] Synthesis Path-Downstream   1~72

  • 1
  • [ 591-18-4 ]
  • [ 122-39-4 ]
  • [ 78600-33-6 ]
YieldReaction ConditionsOperation in experiment
93% With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate; In toluene; at 100℃; for 12h;Inert atmosphere; General procedure: General procedure for the palladium-catalyzed reaction A solution of Pd(OAc)2 (0.8 mg, 0.0036 mmol), Xantphos (2.1 mg, 0.0036 mmol), NaOtBu (51 mg, 0.53 mmol), 1-bromo-4-iodobenzene (1a) (100 mg, 0.35 mmol), and N,N-diphenylamine (2a) (72 mg, 0.43 mmol) in toluene (0.5 mL) was stirred at 100 C for 12 h. The reaction was quenched with H2O, and extracted with CH2Cl2 (3*3 mL). The chemoselectivity (3aa/4aa=92/8) was measured by HPLC analysis using Inertsil ODS-3V. The pure monoaminated product 3aa (99 mg, 86%) was obtained by flash chromatography (hexane/CH2Cl2=97/3) as a white solid.
91% With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate; In toluene; for 2h;Reflux; Diphenylamine in a 2L reactor60.0 g (355 mmol),1-Bromo-3-iodobenzene100.3 g (355 mmol),0.8 g (4 mmol) of palladium acetate,Xantphos 2 g (4 mmol),Sodium tert-butoxide68.2 g (709 mmol),Add 700 mL of toluene,The mixture was stirred under reflux for 2 hours.After the reaction was completed, it was filtered at room temperature and then concentrated under reduced pressure.Separation by column chromatography gave 97 g of Intermediate 4-b .(Yield 91.2%)
91.2% With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; sodium t-butanolate; In toluene; for 2h;Reflux; Diphenylamine (60.0 g, 355 mmol), 1-bromo-3-iodobenzene (100.3 g, 355 mmol), palladium acetate (0.8 g, 4 mmol), xantphos (2 g, 4 mmol), sodium tert-butoxide (68.2 g, 709 mmol), and toluene (700 mL) were placed in a 2 L reactor. The mixture was refluxed with stirring for 2 h. After completion of the reaction, the reaction mixture was filtered at room temperature, concentrated under reduced pressure, and purified by column chromatography to afford Intermediate 4-b (97 g, yield 91.2%).
69% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 70℃; After the starting material diphenylamine (CAS Registry Number: 122-39-4) (7.93 g, 43.86 mmol) was dissolved in toluene (390 ml) in a round bottom flask, 1-bromo-3-iodobenzene (CAS Registry Number: 591-18-4) (19.89 g, 70.29 mmol), Pd2(dba)3 (1.29 g, 1.41 mmol), 50% P(t-Bu)3 (1.8 ml, 3.75 mmol) and NaOt-Bu (13.51 g, 140.58 mmol) are added, and stirred at 70 C. After completion of the reaction, the reaction product was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.48 g (yield: 69%) of the product.

  • 2
  • [ 121-43-7 ]
  • [ 107-21-1 ]
  • [ 78600-33-6 ]
  • [ 871344-03-5 ]
  • 3
  • [ 78600-33-6 ]
  • tris(3-diphenylaminophenyl)amine [ No CAS ]
  • 4
  • [ 78600-33-6 ]
  • N-(3-(2-pyridyl)phenyl)-N,N-diphenylamine [ No CAS ]
  • 5
  • [ 78600-33-6 ]
  • [ 871344-04-6 ]
  • 6
  • [ 78600-33-6 ]
  • N-(3-(isoquinolin-1-yl)phenyl)-N,N-diphenylamine [ No CAS ]
  • 7
  • [ 78600-33-6 ]
  • N-(3-(5-phenylpyridin-2-yl)phenyl)-N,N-diphenylamine [ No CAS ]
  • 8
  • [ 1662-01-7 ]
  • [ 78600-33-6 ]
  • [ 1009362-86-0 ]
  • 9
  • [ 55305-43-6 ]
  • [ 78600-33-6 ]
  • [ 332411-20-8 ]
  • 10
  • [ 108-36-1 ]
  • [ 122-39-4 ]
  • [ 78600-33-6 ]
YieldReaction ConditionsOperation in experiment
55% With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine; In toluene; for 12h;Reflux; [Preparation Example 1] Preparation of compound 1[82][83][84]Preparation of compound 1-1[85]After diphenylamine (20 g, 118.2 mmol), 1,3-dibromobenzene (43 mL, 354.6 mmol), Pd2dba3(2.1g,2.4mmol), tri-O-tolyphosphine (1.8 g,5.9 mmol) and Nat-BuO (22.7 g,2236.4 mmol) were dissolved in toluene (600 mL), the mixture was stirred under reflux for 12 hours. Upon completion of the reaction, extracting with EA and distilled water followed by column separation gave a compound 1-1 (21.1 g, 55%).
48% With tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine; sodium t-butanolate; In toluene; for 12h;Reflux; above, 24.9 mL (206.83 mmol) of 1,3-dibromobenzene, 10 g (59.095 mmol) of diphenylamine, 899 mg of tri- o-tolyphosphine Tris (dibenzylideneacetone) dipalladium (O) (0) was obtained by dissolving 11.4 g (118.19 mmol) of sodium tert-butoxide in toluene, : Pd2 (dba) 3] catalyst for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography with n-hexane. The solution was distilled under reduced pressure,And recrystallized in a solvent of methylene chloride and petroleum ether to obtain 9.26 g (yield: 48%) of compound X1.
  • 11
  • [ 5419-55-6 ]
  • [ 78600-33-6 ]
  • [ 943899-12-5 ]
YieldReaction ConditionsOperation in experiment
69% Preparation of compound 1-2[87]After the compound 1-1 (21.1 g, 65.6 mmol) was dissolved in THF (325 mL) and cooled at -78 C, n-BuLi (31.2 mL, 2.5M in hexane, 78.7 mmol) was slowly added. 1 hour later, triisopropylborate (22.4 mL, 98.4 mmol) was added. After slowly raising the temperature, the mixture was stirred for 12 hours at room temperature. Upon completion of the reaction, extracting with EA and distilled water followed by recrystallization (MC/Hexane) gave a compound 1-2 (13 g,69%).
Compound E3 can be synthesized by a person of ordinary skill following Scheme 12 illustrated in FIG. 13. In the first step compound SI 2-1 is combined with S0Cl2. The intermediate is taken without purification and combined with PhMgBr in THF at 0C and stirred for 4 hours to give compound S I 2-2. In the second step, compound SI 2-3 (available for purchase from Sigma-Aldrich Co., CAS No. 78600-33-6) is added to hexanes and cooled to 0 C before dropwise addition of nBuLi. B(OiPr)3 is subsequently added and the reaction is allowed to stir for 1 hour before being quenched with aqueous HC1 to give compound SI 2- 4. In the third step, compound S I 2-4 and compound SI 2-3 are combined with Pd(OAc)2 and K3P04 in THF at 45 C and stirred for 24 hours to give compound E3. It is understood that steps 1, 2, and 3 can be performed and optimized by a person having ordinary skill in the art without undue experimentation.
  • 12
  • [ 78600-33-6 ]
  • [ 1300610-80-3 ]
  • 13
  • [ 78600-33-6 ]
  • [ 1300610-20-1 ]
  • 14
  • copper(l) cyanide [ No CAS ]
  • [ 78600-33-6 ]
  • [ 332411-20-8 ]
  • 15
  • [ 78600-33-6 ]
  • [ 356060-70-3 ]
  • 16
  • [ 78600-33-6 ]
  • [ 1309459-82-2 ]
  • 17
  • [ 78600-33-6 ]
  • [ 1309459-85-5 ]
  • 18
  • [ 78600-33-6 ]
  • [ 1309459-77-5 ]
  • 19
  • [ 61676-62-8 ]
  • [ 78600-33-6 ]
  • [ 915088-14-1 ]
YieldReaction ConditionsOperation in experiment
58% issolve <strong>[78600-33-6]3-bromo-N,N-diphenylaniline</strong> (1.62g, 5mmol)40 mL of freshly steamed tetrahydrofuran was placed in a low temperature reactor at -78 C for 10 min.After degassing three times with freezing, 3 mL of n-butyllithium (2.40 M, 7 mmol) was slowly added dropwise.After activation for 4 h, slowly add about 2 mL of isopropanol pinacol borate (7 mmol).Stir at room temperature for 48 h.The mixture was extracted with dichloromethane and concentrated to give a crude product.Purification by column chromatography (petroleum ether: methylene chloride = 1: 2) gave white solid (0.84 g,yield: 58%).
  • 20
  • [ 78600-33-6 ]
  • [ 1361051-56-0 ]
  • 21
  • [ 78600-33-6 ]
  • [ 1361051-57-1 ]
  • 22
  • [ 78600-33-6 ]
  • [ 1361051-58-2 ]
  • 23
  • [ 78600-33-6 ]
  • [ 1361051-55-9 ]
  • 24
  • [ 7751-38-4 ]
  • [ 78600-33-6 ]
  • [ 1376938-20-3 ]
YieldReaction ConditionsOperation in experiment
84.1% In a nitrogen atmosphere, 2.0 ml (3.34 mmol) of 1.67 mM n-butyl lithium was added to 976.0 mg (3.01 mmol) of m-bromotriphenylamine at -78C in a tetrahydrofuran solvent, followed by stirring for 30 minutes. Then, 881.3 mg (4.79 mmol) of diisopropyldichlorosilane was added. The resulting mixture was heated gradually and stirred overnight. After water and toluene were added to the solution thus obtained, the organic layer was extracted from the resulting mixture by a separating operation. The solution thus obtained was dried over magnesium sulfate and concentrated under reduced pressure by using a rotary evaporator. The residue was purified using HPLC to yield 950.6 mg (2.53 mmol) of a yellow liquid in a yield of 84.1%. It was confirmed as a result of measurement of GC-MS spectrum that the liquid thus obtained was m-(hydroxydiisopropylsilyl)phenyldiphenylamine. GC-MS m/z: 375 (M+)
  • 25
  • [ 1075-49-6 ]
  • [ 78600-33-6 ]
  • [ 1352089-30-5 ]
  • 26
  • [ 1075-49-6 ]
  • [ 78600-33-6 ]
  • [ 1352089-29-2 ]
  • 27
  • [ 107-21-1 ]
  • [ 78600-33-6 ]
  • [ 871344-03-5 ]
YieldReaction ConditionsOperation in experiment
88% 0.45 g of magnesium and 5 ml of THF were suspended, and a tiny amount of 1,2-dibromoethane was added to the obtained suspension. A mixed solution of 3.0 g of <strong>[78600-33-6]3-bromo-N,N-diphenylaniline</strong> and 30 mL of THF was dripped to this suspension, and the mixture was stirred while being heated under reflux for 1.5 hours to cause a reaction. After the reaction, the solution which was naturally cooled to room temperature was cooled to -78 C., and 1.95 g of trimethyl borate was added thereto. The mixture was stirred while the temperature was increased to room temperature to cause a reaction. After the reaction, the solution was concentrated, and 4.8 mL of ethylene glycol and 30 mL of toluene were added to the obtained residue. The mixture was stirred while being heated under reflux for 12 hours to cause a reaction. After the reaction, the solution was filtered and the obtained filtrate was concentrated, so that a while solid was obtained (88% yield). The synthesis scheme of Step 1 is shown by (a-1).
  • 28
  • [ 1569852-62-5 ]
  • [ 78600-33-6 ]
  • [ 1569852-71-6 ]
  • 29
  • [ 1447669-03-5 ]
  • [ 78600-33-6 ]
  • [ 1569852-65-8 ]
  • 30
  • [ 78600-33-6 ]
  • [ 1542164-20-4 ]
  • 31
  • [ 78600-33-6 ]
  • [ 73183-34-3 ]
  • [ 915088-14-1 ]
YieldReaction ConditionsOperation in experiment
38% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 80℃; for 10h;Inert atmosphere; A mixture of 10 g of 3-bromo-N, N-diphenylaniline,11.7 g of bispinacolato diboron,9.1 g of KOAc and 0.76 g of [1,1'-bis (biphenylphosphino) ferrocene] dichloropalladium (II) [Pd (dppf) Cl2]And 100 ml (ml) of DMSO were placed in a round bottom three-necked flask under a nitrogen atmosphere,And stirred at 80 C for 10 hours.The reaction solution was cooled and extracted with dichloromethane and water,And concentrating the extracted solution. The concentrated solution was subjected to column chromatography using a mixed solvent of dichloromethane and n-hexane and concentrated to give 3.9 g of N, N-diphenyl-3- (4,4,5,5-tetramethyl- 1,3,2-dioxaborane-2-yl) aniline (yield 38%).
38% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In dimethyl sulfoxide; at 80℃; for 10h;Inert atmosphere; 10 g of <strong>[78600-33-6]3-bromo-N,N-diphenylaniline</strong>, 11.7 g of bis(pinacolato)diboron, 9.1 g of potassium acetate,0.76 g of [1,1-bis(biphenylphosphino)ferrocene]dichloromethane (II),100 ml of DMSO was placed in a round bottom three-necked flask under a nitrogen atmosphere and stirred at 80C for 10 hours.The reaction solution was cooled and extracted with dichloromethane and water.The extracted solution was concentrated, and then the concentrated solution was subjected to column chromatography using a mixed solvent of dichloromethane and n-hexane and concentrated to thereby obtain 3.9 g of N,N-diphenyl-3-(4,4,5). , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (yield: 38%).
  • 32
  • 5-phenyl-5,14-dihydrobenzo[a]indolo[3,2-c]carbazole [ No CAS ]
  • [ 78600-33-6 ]
  • C46H31N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
2.18 g With tris-(dibenzylideneacetone)dipalladium(0);  di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; sodium t-butanolate; In o-xylene; for 3h;Reflux; Inert atmosphere; Then, a mixed solution of 2.0 g of intermediate F, 1.86 g of <strong>[78600-33-6]3-bromotriphenylamine</strong>, 60 mg of bis(dibenzylidene acetone) palladium, 74 mg of di-t-butyl (2,2-diphenyl-1-methyl-1-cyclopropyl) phosphine, 604 mg of sodium tert-butoxide, and 26 ml of orthoxylene was heated while stirring for 3 hours under reflux in a flow of nitrogen. After cooling to room temperature, 26 ml of purified water was added and the solution was subjected to celite filtration. The organic layer was dried with magnesium sulfate, followed by filtration and evaporation. The resulting condensate was purified by silica gel column chromatography and liquid was evaporated, followed by vacuum-drying the resulting solid to provide 2.18 g of compound [3]. The resulting powder was subjected to 1H-NMR analysis and the following results were obtained, showing that the white solid obtained above was compound [3]. 1H-NMR (CDCL3 (d=ppm)): 6.61-6.64 (d, 1H, J=8.1), 6.90-7.70 (m, 28H), 8.60-8.63 (m, 1H), 8.96-8.99 (d, 1H, J=8.37).
YieldReaction ConditionsOperation in experiment
68% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 70℃; General procedure: Is the starting material a diphenylamine (73.58g, 434.8mmol) senses a rotation velocity of the disk to a toluene in in round bottom flask , 1-bromo-4-iodobenzene (264.02g, 869.6mmol), Pd 2 (dba) 3 (11.94g, 13mmol), 50% P (t-Bu) 3 (17 ml, 34.8mmol), NaO t-Bu (125.37g, 1304.5mmol) adding an 70 C stirring section. When reaction is completed CH 2 Cl 2 and a water extraction of organic layer after MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 112.78g (yield: 80%)is obtained.
67% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 70℃; General procedure: The M 1-1 (45.05 g, 266.2 mmol) to a round bottom flask was charged with toluene (2000 ml) to dissolve after, 1-bromo-4-iodobenzene (150.63 g, 532.4 mmol), Pd2(dba)3 (7.31 g, 8 mmol), was 50% P(t-Bu)3 (10.4 ml, was added to 21.3 mmol), NaOt-Bu (76.76 g, 798.7 mmol) and stirred at 70C. After the reaction was completed CH2Cl2. And extracted with water, the organic layer was dried with MgSO4 and concentrated to produce the compound and then a silicagel column and the product was recrystallized from 63.01 g (yield: 73%) was obtained.
66% With copper(l) iodide; 1,10-Phenanthroline; potassium hydroxide; In 5,5-dimethyl-1,3-cyclohexadiene; for 18h;Reflux; General procedure: L round bottom flask formula diphenyl amine 20 g (118 mmol), 1- bromo-4-iodo-benzene 33.4 g (118mmol), potassium hydroxide 13.2 g (236 mmol) the mixture was stirred into 400 ml of xylene. 1,10 nansseu page in five minutesAnd stirred to give after adding a rolrin gave 7 g (35.5 mmol). If the materials are somewhat rust Cooper iodide 6.75 g(35.5 mmol) was added raising the temperature back to the mixture was heated under reflux for 18 hours. Using ethyl acetate and water to the impuritiesGave was removed after the removal of water into the anhydrous magnesium sulfate. The filter is then the solution of ethyl acetate and ethanolUsing recrystallization to give the formula M 2-1 24 g (63%)
55% With 1, 3-(di(dicyclohexyl)phosphinyl-2-(2?-N, N-dimethylamine)phenyl)indene; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In N,N-dimethyl-formamide; at 120℃; for 12h; General procedure: The stirring method in the reaction bottle can be sealed, by adding 0.01 millimole Pd (dba)2, 1.3 sodium butylatelong and fine hair mole of uncle, 0.02 long and fine hair mole of phosphine ligand (phosphine ligand A, C, E consumption is 0.02 mmol, the metallisation B, D, F consumption is 0.01 mmol), 1.2 mmol paradichlorbenzene and 1.0 millimole diphenylammonium, then adding solvent 1.5 ml of ethylene glycol dimethyl ether. Sealing reaction bottle, in the 120 C reaction 12 hours, after cooling, the product is extracted with ethyl acetate, washing of the organic layer with water, ethyl acetate vacuum, the crude product is alumina column separation obtain the high-purity product. different phosphine and palladium catalytic the catalyst formed by the reaction of the triphenylamine, can get the medium to the high yield, the metallisation with D the highest activity of the catalyst of the Pd, the result shown in table 1
40% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 1h;Inert atmosphere; General procedure: Dibromobenzene (17.69g, 75mmol), sodium tetrabutoxide (21.62g, 22mmol), toluene (500mL) in a 3-neck flask under nitrogen conditions.Dibenzeneamine (12.69g, 75mmol) and catalyst Pd2 (dba) 3 (2.06g, 2.25mmol) were added, N2 was replaced three times, tritetrabutylphosphine (0.36mL, 15mmol) was poured, and the mixture was Heated at 110 C. for 1 hour. The reaction solution was cooled, washed with water, and recrystallized with DCM / PE to obtain a yellow solid. Again, wash with toluene / EA mixed solution at 45 C. for 2 hours and filter to obtain A-1 (9.48 g, 39%).The obtained compound was confirmed by LC-MS.

  • 34
  • C30H18N2O [ No CAS ]
  • [ 78600-33-6 ]
  • C48H31N3O [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 12h;Reflux; Inert atmosphere; In a three-neck flask, 2.11 g (5 mmol) of compound (1-4), 1.78 g (5.5 mmol) of <strong>[78600-33-6]3-bromotriphenylamine</strong>, 90 mg (0.1 mmol) of Pd2(dba)3, 0.12 g (0.4 mmol) of tri-t-butylphosphonium tetrafluoroborate, 0.67 g (7 mmol) of sodium t-butoxide and 30 mL of dehydrated toluene were placed. The resultant was reuxed in an argon atmosphere for 12 hours. After completion of the reaction, insoluble matters were separated by filtration through celite. The filtrate was transferred to a dripping funnel and extracted several times with toluene. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered and concentrated. The resultant was puried by silica gel chromatography (hexane:toluene=5:2), whereby white solids were obtained. The yield was 2.40 g and the percentage yield was 72%.
  • 35
  • C36H20N2O2 [ No CAS ]
  • [ 78600-33-6 ]
  • C54H33N3O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 20h;Reflux; Inert atmosphere; In a three-neck flask, 2.56 g (5 mmol) of compound(7-1), 1.78 g (5.5 mmol) of <strong>[78600-33-6]3-bromotriphenylamine</strong>, 90 mg (0.1 mmol) of Pd2(dba)3, 0.12 g (0.4 mmol) of tri-t-butylphosphonium tetrafluoroborate, 0.67 g (7 mmol) of sodiumt-butoxide and 30 mL of dehydrated toluene were placed. The resultant was refluxed in an argon atmosphere for 20 hours.[0209] After completion of the reaction, insoluble matterswere separated by ltration through celite. The ltrate wastransferred to a dripping furmel and extracted several timeswith toluene. An organic phase obtained was dried with anhy-drous magnesium sulfate, ltered and concentrated. Theresultant was puried by silica gel chromatography (hexane:toluene~3:1), whereby white solids were obtained.[0210] The yield was 2.83 g and the percentage yield was75%
  • 36
  • [ 78600-33-6 ]
  • C45H34N2 [ No CAS ]
  • 37
  • [ 23561-28-6 ]
  • [ 7732-18-5 ]
  • [ 78600-33-6 ]
  • [ 943899-12-5 ]
YieldReaction ConditionsOperation in experiment
60% As shown in Scheme 5 above, 8.9 g (27.451 mmol) of compound X2 is dissolved in tetrahydrofuran (THF). After lowering the temperature to -78 C, slowly add 14.3 mL of a 2.5 M solution of n-butyllithium (n-BuLi). The mixture is stirred at room temperature for 1 hour after dropwise addition. Lower the temperature again to -78 C and add 7.0 mL (41.176 mmol) of triethyl borate slowly. The mixture is stirred at room temperature for 12 hours after dropwise addition. After 12 hours, add 50 mL of 5 N hydrochloric acid (HCl) solution, remove tetrahydrofuran (THF), and extract with distilled water and methylene chloride. The solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography with methylene chloride. The solution was distilled under reduced pressure to obtain 4.75 g (yield: 60%) of compound X3.
  • 38
  • 5-(3,5-diphenyltriazine 2-yl)-10H-dihydrophenazine [ No CAS ]
  • [ 78600-33-6 ]
  • C45H32N6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With copper; sodium t-butanolate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask was added the compound (3) 0.1 Lmol 3, Compound (4) 0.1 Lmol, 1mol of sodium tert-butoxide, 0.02mol copper catalyst and toluene (1000mL), was heated at reflux under nitrogen for 24 hours, cooling, toluene was removed, dichloromethane was added, washed with water, dried, the crude product by column with dichloromethane and recrystallized from ethanol to give compound A, yield 82% (C45H32N6Mu = 656.27, the detected amount = 417.3).
  • 39
  • [ 1060735-14-9 ]
  • [ 78600-33-6 ]
  • C48H33N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
17.0 g With  di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In o-xylene; for 2h;Reflux; Inert atmosphere; Then,9-phenyl-9H, 9'H-3,3'-carbazole 11.4 g,<strong>[78600-33-6]3-bromotriphenylamine</strong>10.0 g,Bis (dibenzylideneacetone) palladium 161 mg,Di-t-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl) phosphine 198 mg,Sodium butoxide 1.0 gWith o-xylene 140 ml of the mixed solution,And the mixture was heated and stirred under reflux in a nitrogen stream for 2 hours. After cooling to room temperature, the mixture was extracted with toluene 1.0 ml.The organic layer was washed three times with 80 ml of water, dried over magnesium sulfate and evaporated.The resulting concentrate was purified by silica gel column chromatography,The resulting solid was evaporated in vacuo to give a white solid, 17.0 g.
  • 40
  • [ 78600-33-6 ]
  • C49H36N2O [ No CAS ]
  • 41
  • [ 78600-33-6 ]
  • C36H25BrN2 [ No CAS ]
  • 42
  • [ 78600-33-6 ]
  • C54H39N3 [ No CAS ]
  • 43
  • [ 78600-33-6 ]
  • C66H48N4 [ No CAS ]
  • 44
  • [ 78600-33-6 ]
  • [ 62-53-3 ]
  • N<SUP>1</SUP>,N<SUP>1</SUP>,N<SUP>3</SUP>-triphenylbenzene-1,3-diamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Inert atmosphere; Reflux; A mixture of 15 g of 2-bromo-N, N-diphenylaniline,8.6 g of aniline, 0.4 g of Pd2 (dba) 3,0.4 g of P (t-Bu) 3 and13.3 g of Na (t-BuO)Placed in a round bottom three-necked flask in a nitrogen atmosphere,And 100 ml of toluene was added.The mixture was stirred and refluxed. After completion of the reaction,The resulting solution was washed with dichloromethane and water. Collecting organic layer,Dried over MgSO4 and separated by column,Thereby obtaining intermediate 6. (14.6 g, 94% yield)
  • 45
  • [ 78600-33-6 ]
  • [ 709022-63-9 ]
  • 3-(anthracen-9-yl)-N,N-diphenylaniline [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With potassium carbonate; In ethanol; water; toluene; at 90℃; for 24h;Inert atmosphere; The 9 - B - AN (360 mg, 1 . 18 mmol), 3 - bromo-aniline (300 mg, 0 . 93 mmol), potassium carbonate (2.76 g, 20 mmol), 10 ml distilled water, 15 ml toluene, 7.5 ml anhydrous ethanol by adding 100 ml single-port in the bottle, in the stirring, under the protection of nitrogen, 90 C reflux 24 h. After cooling, water is added 30 ml, dichloromethane is used for extraction the aqueous phase several times. Collecting organic phase, evaporation of the solvent the product after the decompression by chromatographic column chromatography purification, petroleum ether/methylene chloride [...] selected 6:1. Vacuum drying to obtain a white powder 286 mg, namely mTPA - 9 - AN, the yield is 73%.
  • 46
  • C30H22N2S [ No CAS ]
  • [ 78600-33-6 ]
  • C48H35N3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; After Sub 1-1 (3.96 g, 8.95 mmol) obtained in the above synthesis was dissolved in toluene (90 ml) in a round bottom flask, Sub 2-1 (2.90 g, 8.95 mmol), Pd2(dba)3 (0.25 g, 0.27 mmol), 50% P(t-Bu)3 (0.3 ml, 0.54 mmol) and NaOt-Bu (2.58 g, 26.84 mmol) are added, and stirred at 100 C. After completion of the reaction, the reaction product was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 5.65 g of the product (yield: 92%).
  • 47
  • [ 78600-33-6 ]
  • C36H26Br2N2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With bis-[(trifluoroacetoxy)iodo]benzene; In 1,2-dichloro-ethane; at 20℃; for 0.5h; General procedure: PIFA (0.75 equiv.) was added to a stirred solution of the appropriatenaphthalenamine 1 (0.30 mmol, 1 equiv) in DCE (3 mL) atr.t., and the mixture was stirred for 30 min. When the reactionwas complete, sat. aq NaHCO3 was added to the mixture, andthe aqueous phase was extracted with CH2Cl2. The extractswere dried (Na2SO4) and evaporated to dryness, and the cruderesidue was purified by column chromatography (silica gel,hexane-EtOAc).
  • 48
  • C29H21N [ No CAS ]
  • [ 78600-33-6 ]
  • C49H34N2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 12h;Inert atmosphere; Under nitrogen, 9.5 g of intermediate 4-4 (20 mmol), 0.13 g of palladium acetate (0.6 mmol), 0.45 g of tri-tert-butyl were added.Phosphine (2.2 mmol), 7.1 g of the compound of formula E-13 (22 mmol), 5.7 g of sodium t-butoxide, 300 mL of toluene, 110 C reactionAfter cooling to room temperature for 12 hours, the mixture was extracted with chloroform and evaporated to remove the solvent, and then the silica gel column was obtained to obtain 12.5 g of solid compound C-89 (yield 87%).
  • 49
  • [ 78600-33-6 ]
  • C58H41N [ No CAS ]
  • 50
  • [ 92855-12-4 ]
  • [ 78600-33-6 ]
  • N1-(2-(naphthalen-1-yl)phenyl)-N3,N3-diphenyl-1,3-phenylenediamine [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 48h;Inert atmosphere; (1) in a 500ml three-necked bottle,Add 2-(naphthalen-1-yl)aniline 21.93 g, 100 mmol),M-bromotriphenylamine (32.42g, 100mmol), sodium tert-butoxide(28.83 g, 300 mmol) was added 100 g of toluene, and palladium acetate was added under the protection of N2.After reacting at 120 C for 48 h, the reaction was completed by TLC.Wash water (200ml) three times, add activated carbon to decolorize,Dry and concentrated to a gray solid, which was crystallized from ethyl acetate.Dry under vacuumN1-(2-(naphthalen-1-yl)phenyl)-N3,N3-diphenyl-1,3,-phenylenediamine39.78 g, 86% yield.
  • 51
  • C22H23BO2 [ No CAS ]
  • [ 78600-33-6 ]
  • C34H25N [ No CAS ]
YieldReaction ConditionsOperation in experiment
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; toluene; for 16h;Reflux; General procedure: 335 g (1.5 mol) of 3-bromo-1-naphthol, 246 g (2.0 mol) of phenylboronic acid, 33.5 g (31.0 mmol) of tetrakis(triphenylphosphine)palladium, 430 g (3.1 mol) of potassium carbonate, 2 L of toluene, 2 L of 1,4-dioxane, and 1 L of water were refluxed in a round-bottom flask for 16 h. After completion of the reaction, the reaction mixture was left standing for layer separation. The organic layer was concentrated under reduced pressure and recrystallized from toluene and methanol to afford 330 g of Intermediate 1-a (yield 75%).
  • 52
  • [ 613-32-1 ]
  • [ 78600-33-6 ]
  • C30H23N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With copper(l) iodide; potassium carbonate; In N,N-dimethyl acetamide; at 160℃; for 12h;Inert atmosphere; (3) 5,10-dihydrophenazine (18.22 g, 100 mmol) was added to a 500 mL three-necked flask.3-bromo-N,N-diphenylamine (32.42 g, 100 mmol),Potassium carbonate (41.46 g, 300 mmol), crown ether (2.64 g, 10 mmol), 200 mL of dimethylacetamide,Nitrogen iodide (1.90 g, 10 mmol) was added, and the temperature was raised to 160 C for 12 h.The liquid phase monitoring reaction is completed, and the temperature is lowered to 50 C.Add intermediate a (44.93 g, 100 mmol),The temperature was raised to 160 C to continue the reaction for 16 h, the liquid phase monitoring reaction was completed, cooled to room temperature, washed with water, filtered,Column chromatography (developing solvent: ethyl acetate: petroleum ether = 1:20) gave 50.81 g of objective compound 39.Yield 64%,
  • 53
  • [ 92-39-7 ]
  • [ 78600-33-6 ]
  • C30H21ClN2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With copper(l) iodide; rac-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane; at 95℃; for 10h;Inert atmosphere; (1) In a 1L reaction flask, add 2-chloro-10H-phenothiazine (46.74 g, 200 mmol), 3-bromo-N, N-diphenylaniline (64.84 g, 200 mmol), and 1,2-cyclo Hexanediamine (2.28g, 20mmol), cuprous iodide (0.76g, 4mmol), sodium tert-butoxide (38.44g, 400mmol), 500g 1,4-dioxane, heated to 95 C under nitrogen protection The reaction was carried out for 10 hours. The reaction was monitored in liquid phase to complete the reaction. The reaction solution was filtered through a silica gel funnel, and the filtrate was washed with water, separated into layers, and concentrated. After beating with petroleum ether and ethyl acetate at 1:10, 71.55 g of intermediate b was obtained with a yield of 75%.
  • 54
  • [ 78600-33-6 ]
  • C30H21ClN2O2S [ No CAS ]
  • 55
  • [ 78600-33-6 ]
  • C48H33N3O2S2 [ No CAS ]
  • 56
  • [ 2304743-93-7 ]
  • [ 78600-33-6 ]
  • [ 2450428-31-4 ]
YieldReaction ConditionsOperation in experiment
13.2 g With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 24h; 66 [Synthesis Example 1] Synthesis of Mat 1 General procedure: Preparation Example 1 250 mL of xylene was added to 3.08g (9.25mmol) and 3.28g (10.17mmol) of 4-bromo-N,N-diphenylaniline.Pd2(dba)3 0.42g (0.46mmol), Xphos 0.44g (0.92mmol), and NaOtBu 2.2g (23.1mol) were added and heated to reflux at 120° C. for 24 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution in the reaction solution. After extracting the mixed solution with 500 mL of M.C,Washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain 4.1 g (yield 77%) of the title compound.
  • 57
  • [ 2304743-91-5 ]
  • [ 78600-33-6 ]
  • [ 2450423-09-1 ]
YieldReaction ConditionsOperation in experiment
13.2 g With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 24h; 26 [Synthesis Example 1] Synthesis of Mat 1 General procedure: Preparation Example 1 250 mL of xylene was added to 3.08g (9.25mmol) and 3.28g (10.17mmol) of 4-bromo-N,N-diphenylaniline.Pd2(dba)3 0.42g (0.46mmol), Xphos 0.44g (0.92mmol), and NaOtBu 2.2g (23.1mol) were added and heated to reflux at 120° C. for 24 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution in the reaction solution. After extracting the mixed solution with 500 mL of M.C,Washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain 4.1 g (yield 77%) of the title compound.
  • 58
  • [ 2304743-92-6 ]
  • [ 78600-33-6 ]
  • [ 2450425-73-5 ]
YieldReaction ConditionsOperation in experiment
13.2 g With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 24h; 46 [Synthesis Example 1] Synthesis of Mat 1 General procedure: Preparation Example 1 250 mL of xylene was added to 3.08g (9.25mmol) and 3.28g (10.17mmol) of 4-bromo-N,N-diphenylaniline.Pd2(dba)3 0.42g (0.46mmol), Xphos 0.44g (0.92mmol), and NaOtBu 2.2g (23.1mol) were added and heated to reflux at 120° C. for 24 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of an aqueous ammonium chloride solution in the reaction solution. After extracting the mixed solution with 500 mL of M.C,Washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain 4.1 g (yield 77%) of the title compound.
  • 59
  • [ 92-67-1 ]
  • [ 78600-33-6 ]
  • [ 1800322-10-4 ]
YieldReaction ConditionsOperation in experiment
55% With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In toluene for 24h; Reflux; 7.1 Synthesis Example 5-(3): Synthesis of Intermediate 5-c General procedure: Add 4.5g (16mmol) of 1-bromo-3-iodobenzene in a 100mL reactor, Aniline 5.8g (16mmol), palladium acetate 0.1g (1mmol), Sodium tert-butoxide 3g (32mmol), bis(diphenylphosphine)-1,1'-binaphthalene 0.2g (1mmol), 45 mL of toluene was refluxed and stirred for 24 hours. After the reaction is complete, filter and concentrate the filtrate, It was separated by column chromatography to obtain 5.2 g of . (Yield 82%)
55% With palladium diacetate; sodium tertiary butoxide In toluene for 24h; Reflux; 8-1 Synthesis Example 6-3. Synthesis of <Intermediate 6-c> General procedure: 1-Bromo-5-iodobenzene (59 g, 177 mmol), 4-tert-butylaniline (58 g, 389 mmol),Palladium acetate (1.6g, 7mmol), Sodium tert-butoxide (51g, 530mmol), Bis(diphenylphosphino)-1,1' -binaphthyl) (4.4 g, 7 mmol) and 500 mL of toluene were placed in a 1 L reactor and stirred under reflux for 24 hours. After the reaction was completed, the filtrate was filtered and concentrated. It was separated by column chromatography to obtain (52.8 g, yield 80%).
  • 60
  • [ 769-92-6 ]
  • [ 78600-33-6 ]
  • [ 2118936-88-0 ]
YieldReaction ConditionsOperation in experiment
40 g With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 2h; Inert atmosphere; B1 Synthesis Example (B1): Synthesis of Compound (1-3001) In a nitrogen atmosphere, 3-bromo-N,N-diphenylaniline (35g), 4-tert-butylaniline (19.3g), Dichlorobis[(di-tert-butyl(4-dimethylaminophenyl)phosphino)]palladium (Pd-132, 76mg) as a palladium catalyst, Sodium tert-butoxide (NaOtBu, 15.6g) and xylene (200ml) were put into the flask and heated at 120°C for 2 hours. After the completion of the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. After that, the crude product obtained by concentrating the organic layer was purified using a short silica gel column (eluent: toluene/heptane=1/1 (volume ratio)) to obtain an intermediate (I-1) 40g.
1.4 g With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; Inert atmosphere; B2 Synthesis Example (B2): Synthesis of Compound (2-52) Under a nitrogen atmosphere, 3-bromo-N,N-diphenylaniline (35 g), 4-t-butylaniline (19.3 g), and dichlorobis[(di-t-butyl(4-dimethylaminophenyl)phosphino) as a palladium catalyst. Palladium (Pd-132, 76 mg), sodium-t-butoxide (NaOtBu, 15.6 g) and xylene (200 ml) were placed in a flask and heated at 120° C. for 2 hours.After completion of the reaction, water and ethyl acetate were added to the reaction mixture and the mixture was stirred, and then the organic layer was separated and washed with water.After that, the crude product obtained by concentrating the organic layer was purified with a silica gel short column (eluent: toluene/heptane = 1/1 (volume ratio)) to obtain intermediate (I-1) (40 g). Obtained.
40 g With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; Inert atmosphere; Synthesis Example (B2): Synthesis of Compound (D-52) nder nitrogen atmosphere, 3-bromo-N, N-diphenylaniline (35 g), 4-t-butylaniline (19.3 g), dichlorobis[di-t-butyl(4-dimethylaminophenyl)phosphino]palladium(II) as palladium catalyst (Pd-132, 76 mg), sodium-t-butoxide (NaOtBu, 15.6 g) and xylene (200 ml) were put in a flask and heated at 120°C for 2 hours.After completion of the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water.Thereafter, the crude product obtained by concentrating the organic layer was purified by a silica gel short column (eluent: toluene/heptane = 1/1 (volume ratio)) to obtain an intermediate (I-1) (40 g).
  • 61
  • [ 2666326-92-5 ]
  • [ 78600-33-6 ]
  • [ 2666326-96-9 ]
YieldReaction ConditionsOperation in experiment
75% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 90℃; for 10h; 9.1 Step 1: Preparation of compound Int.-16 11.8g (40.0mmol) of intermediate Int.-12 was mixed with 50mL of toluene, and 48.0mmol of 3-bromo-N,N-diphenylaniline, 5.8g (60.0mmol) of sodium tert-butoxide, 183.2mg were added (0.2mmol) of Pd2(dba)3 catalyst and 0.5mL of 10% tri-tert-butylphosphorus toluene solution, heated to 90°C and stirred for 10 hours. After the reaction, 50mL of water was added to separate the organic phase and the water phase It was extracted with ethyl acetate, the organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure, and separated and purified with a silica gel column to obtain Int.-16 with a yield of 75%.
  • 62
  • [ 78600-33-6 ]
  • [ 74357-31-6 ]
  • [ 2677760-86-8 ]
YieldReaction ConditionsOperation in experiment
75% With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 18h; Inert atmosphere; 9 Example 9 (Synthesis of compound (A64)) Compound (9) (2.00 g, 7.43 mmol), 3-bromotriphenylamine (2.53 g, 7.80 mmol) obtained in Synthesis Example 3 under an argon atmosphere,Tris (dibenzylideneacetone) bispalladium (140 mg, 0.15 mmol), tri-tert-butylphosphonium = tetrafluoroborate (190 mg, 0.67 mmol) and sodium-tert-butoxide (1.21 g, 12.6 mmol) were suspended in toluene (25 mL).The mixture was stirred at 110 ° C. for 18 hours. After allowing to cool to room temperatureToluene was added to the reaction mixture and the mixture was filtered through Celite.The crude product obtained by distilling off the solvent is purified by silica gel column chromatography (hexane / chloroform).A white powder of the target compound (A64) was obtained (2.87 g, 5.60 mmol, yield 75%).
  • 63
  • [ 2760143-07-3 ]
  • [ 78600-33-6 ]
  • [ 2760142-80-9 ]
YieldReaction ConditionsOperation in experiment
67.9% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 90℃; I.8.3 (3) Sub 1-62 synthesis Sub 1-62b (20 g, 34 mmol) and 3-bromo-N,N-diphenylaniline (11.5 g, 35.7 mmol), Pd2(dba)3 (0.9 g, 1 mmol),50% P(t-Bu)3 (0.4 ml, 2 mmol) and NaOt-Bu (9.8 g, 102 mol) were added to toluene (349 ml) and stirred at 90°C. Upon completion of the reaction, 19.2 g (67.9%) of Sub 1-62 was obtained by using the separation method described in the synthesis of Sub 1-3a.
  • 64
  • [ 2725824-88-2 ]
  • [ 78600-33-6 ]
  • [ 2725824-77-9 ]
YieldReaction ConditionsOperation in experiment
87.5% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 135℃; for 6h; II.7 7. P-53 Synthesis Example Sub1-1 (30 g, 0.06 mol), Sub2-28 (18.7 g, 0.06 mol), Pd2(dba)3(1.6 g, 0.0018 mol), NaOt-Bu (17 g, 0.18 mol), P(t- Bu)3 (1.4 g, 0.0035 mol) and Toluene (120 mL) were added and reacted at 135°C for 6 hours. When the reaction was completed, 38 g (87.5%) of the product P-53 was obtained by using the separation method for P-1 described above.
  • 65
  • [ CAS Unavailable ]
  • [ 78600-33-6 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
75% With copper (I) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene at 100℃; for 24h; Inert atmosphere; 7.2 2) under nitrogen atmosphere, in reaction flask, add reaction solvent 1,2-dichlorobenzene, add reaction intermediate C93 (2mmol) successively, reactant D93 (2mmol), potassium carbonate (8mmol), catalyst CuI (0.4 mmol) and ligand 18-crown-6 (0.4 mmol), the temperature was raised to 100 °C, and the reaction was carried out for 24 h. After the reaction is completed, cool to room temperature, collect the organic phase by suction filtration, add dichloromethane/H2O for extraction, dry the collected organic phase with anhydrous Na2SO4, collect the filtrate by suction filtration, remove the solvent and carry out column chromatography purification , to obtain compound M93 (yield 75%).
  • 66
  • [ 2767023-17-4 ]
  • [ 78600-33-6 ]
  • [ 2767023-18-5 ]
YieldReaction ConditionsOperation in experiment
59% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 120℃; for 2h; Inert atmosphere; 1 General procedure for synthesis A A V2: General procedure: 11 (1.20 equivalents), E2 (1.00 equivalents), tris(dibenzylideneacetone)dipalladium Pd2(dba)s (0.02 equivalents; CAS: 51364-51-3), tri-tert-butyl-phosphine (PfBu)s, CAS: 13716-12-6 , 0.08 equivalents) and sodium tert-butoxide (NaO'Bu; 2.00 equivalents) are stirred under nitrogen atmosphere in toluene at 120 °C for 2 h. After cooling down to room temperature (rt) the reaction mixture is extracted with toluene and brine and the phases are separated. The combined organic layers are dried over MgSC and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and I2 is obtained as solid.
  • 67
  • [ 2762059-46-9 ]
  • [ 78600-33-6 ]
  • [ 2762058-40-0 ]
YieldReaction ConditionsOperation in experiment
73% With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane for 5h; Reflux; 9 Synthesis of compound 1-1: Dissolve 0.007mol of intermediate 1-1-1 in 40ml of 1,4-dioxane solvent, stir under nitrogen, and add 0.007mol of 2-chloro-4,6 in turn -Diphenyl-1,3,5-triazine, 0.018mol of K2CO3, 0.1mmol of tetrakis(triphenylphosphine)palladium, heat up to reflux reaction, after 5h, HPLC detects that the reaction of the raw materials is basically completed, and the reaction solution is decompressed and rotated After drying, the residue was subjected to column chromatography to obtain a yellow solid and cooled to room temperature. 100 mL of deionized water was added for hydrolysis, stirred for 10 minutes, and the layers were separated. The organic phase was washed three times with toluene, and the organic phases were combined and dried over anhydrous magnesium sulfate. The desiccant was filtered off, the solvent was spin-dried, and the residue was separated by silica gel column chromatography to obtain a pale yellow solid (yield 74%)
  • 68
  • [ 135-67-1 ]
  • [ 78600-33-6 ]
  • [ 2809368-82-7 ]
YieldReaction ConditionsOperation in experiment
82% With tripotassium phosphate tribasic; copper (I) iodide; N<SUP>1</SUP>,N<SUP>2</SUP>-bis(furan-2-ylmethyl)oxalamide In sulfolane at 100℃; for 18h; Inert atmosphere; Sealed tube;
  • 69
  • [ 2816991-64-5 ]
  • [ 78600-33-6 ]
  • [ 2816991-13-4 ]
YieldReaction ConditionsOperation in experiment
59.4% With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene for 11h; Inert atmosphere; Reflux; 8 Example 8: Preparation of Compound B-199 Under nitrogen protection, N (24 g, 50 mmol), 3-bromo-N,N-diphenylaniline (24.3 g, 75 mmol), and tris(dibenzylideneacetone)bispalladium (0.23 g, 0.25 mmol) were combined , Sphos (2 g, 5 mmol) and sodium tert-butoxide (14.4 g, 150 mmol) were dissolved in 200 ml of xylene, and the mixture was stirred at reflux for 11 hours.After the completion of the reaction, add water and liquid, extract the aqueous phase with ethyl acetate, and perform column chromatography separation after concentration to obtain 21.5 g of solid with a yield of 59.4%.
  • 70
  • [ 2176462-87-4 ]
  • [ 78600-33-6 ]
  • [ 2396537-99-6 ]
YieldReaction ConditionsOperation in experiment
72.6 % With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In o-xylene at 190℃; 9 [Example 9] Preparation of Compound H1-36 14H-7b,14-diazadibenzo[3,4:5,6]azuleno[7,8,1-Ima]fluorene (5.0 g, 15.1 mmol), 3-bromo-N,N-diphenylaniline (5.4 g, 16.6 mmol), Pd2(dba)3 (0.693 g, 0.757 mmol), Sphos (0.621 g, 1.51 mmol), NaOt-Bu (3.64 g, 37.8 mmol), and 60 mL of o-xylene were added to a flask, dissolved, and then stirred under reflux at 190° C. for an hour. After completion of the reaction, the mixture was cooled to room temperature, and separated by silica filter to obtain compound H1-36 (6.3 g, yield: 72.6%).
72.6 % With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In o-xylene at 190℃; 9 [Example 9] Preparation of Compound H1-36 14H-7b,14-diazadibenzo[3,4:5,6]azuleno[7,8,1-Ima]fluorene (5.0 g, 15.1 mmol), 3-bromo-N,N-diphenylaniline (5.4 g, 16.6 mmol), Pd2(dba)3 (0.693 g, 0.757 mmol), Sphos (0.621 g, 1.51 mmol), NaOt-Bu (3.64 g, 37.8 mmol), and 60 mL of o-xylene were added to a flask, dissolved, and then stirred under reflux at 190° C. for an hour. After completion of the reaction, the mixture was cooled to room temperature, and separated by silica filter to obtain compound H1-36 (6.3 g, yield: 72.6%).
  • 71
  • [ 78600-33-6 ]
  • [ 2883571-59-1 ]
  • [ 2883571-60-4 ]
YieldReaction ConditionsOperation in experiment
80 % With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; Inert atmosphere; 7 Example 7 In an argon atmosphere, add 1-1 (6.5 g, 20.0 mmol), 7-1 (9.9 g, 30.0 mmol), tris(dibenzylideneacetone) palladium (274.7 mg, 0.3 mmol), tri-tert-butylphosphonium tetrafluoroborate (348.2 mg, 1.2 mmol), sodium tert-butoxide (3.8 g, 40.0 mmol) and 40 mL anhydrous toluene to 110 °C and stir the reaction for 14 hours. After the reaction was cooled to room temperature, diluted with ether, saturated ammonium chloride aqueous solution was washed three times, organic phase was collected, anhydrous sodium sulfate was dried, concentrated under reduced pressure, and the crude product was separated by silica gel column to obtain product 7-2 (8.6g, yield: 75%).
  • 72
  • [ 78600-33-6 ]
  • [ 5905-36-2 ]
  • [ 2883571-33-1 ]
YieldReaction ConditionsOperation in experiment
95 % With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; Inert atmosphere; 1 Example 1: In an argon atmosphere, add 1-1 (13.0 g, 40.0 mmol), 1-2 (5.2 g, 20.0 mmol), tris(dibenzylideneacetone)dipalladium (549.4 mg, 0.6 mmol), tri-tert-butylphosphonium tetrafluoroborate (696.3 mg, 2.4 mmol), sodium tert-butoxide (7.7 g, 80.0 mmol) and 80 mL anhydrous toluene to 110 °C and stir the reaction for 14 hours. After the reaction was cooled to room temperature, diluted with ether, saturated ammonium chloride aqueous solution was washed three times, organic phase was collected, anhydrous sodium sulfate was dried, concentrated under reduced pressure, and the crude product was separated by silica gel column to obtain products 1-3 (14.2g, yield: 95%).
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