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Chemical Structure| 870774-25-7 Chemical Structure| 870774-25-7

Structure of 870774-25-7

Chemical Structure| 870774-25-7

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Product Details of [ 870774-25-7 ]

CAS No. :870774-25-7
Formula : C16H13BO2
M.W : 248.08
SMILES Code : C1(=CC=CC2=CC=CC=C12)C3=CC=C(C=C3)B(O)O
MDL No. :MFCD08669639
InChI Key :BQHVXFQXTOIMQM-UHFFFAOYSA-N
Pubchem ID :44119399

Safety of [ 870774-25-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 870774-25-7 ] Show Less

Physicochemical Properties

Num. heavy atoms 19
Num. arom. heavy atoms 16
Fraction Csp3 0.0
Num. rotatable bonds 2
Num. H-bond acceptors 2.0
Num. H-bond donors 2.0
Molar Refractivity 79.21
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

40.46 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

0.0
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

3.7
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

2.19
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

2.72
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

1.93
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.11

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-4.2
Solubility 0.0156 mg/ml ; 0.0000631 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-4.24
Solubility 0.0143 mg/ml ; 0.0000575 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-5.49
Solubility 0.00081 mg/ml ; 0.00000327 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

High
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

Yes
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-5.19 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

0.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

1.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<2.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

2.16

Application In Synthesis of [ 870774-25-7 ]

* 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 [ 870774-25-7 ]

[ 870774-25-7 ] Synthesis Path-Downstream   1~35

  • 1
  • [ 870774-25-7 ]
  • [ 1714-29-0 ]
  • 1-(4-naphthalene-1-yl-phenyl)pyrene [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 8h;Heating / reflux; (Synthesis of Compound (AN-2)) (1) Synthesis of Intermediate [1-bromo-6-(4-naphthalene-1-yl-phenyl) pyrene] 7.4 g of 4-(naphthalene-1-yl) phenyl boronic acid prepared by a well known method and 7.0 g of conventional 1-bromopyrene were dissolved in 80 ml of dimethoxyethane (DME). Subsequently, 0.58 g of tetrakistriphenylphosphine palladium and 40 ml of 2M-sodium carbonate aqueous solution were added therein, followed by argon displacement. After heating and refluxing over 8 hours, it was stood to cool and then an organic layer was extracted therefrom by toluene. The organic layer was washed by saturated salt water, followed by drying through anhydrous sodium sulfate, and then the organic solvent was removed by an evaporator. The residue was refined through a silica gel chromatography (a developing solvent: toluene) and then 10.0 g of 1-(4-naphthalene-1-yl-phenyl) pyrene was obtained. (yield: 99 %) 10.0 g of 1-(4-naphthalene-1-yl-phenyl)pyrene obtained was dispersed into 100 ml of dimethyl formaldehyde (DMF), and 5.3 g N-bromosuccinamide (NBS) in DMF solution was dropped therein at room temperature. After stirred over 5 hours, it was left around overnight. After the overnight, 150 ml of water was added to it and the deposited crystal was filtrated, followed by water and ethanol washing of the crystal. The crystal obtained was refined through a silica gel chromatography (a developing solvent: hexane / toluene = 2 / 1) and then 4.5 g of 1-bromo-6-(4-naphthalene-1-yl-phenyl)pyrene (the yield: 38%) and 3.8 g of 1-bromo-8-(4-naphthalene-1-yl-phenyl)pyrene were obtained (the yield: 32%) as the intermediates.
  • 2
  • [ 5419-55-6 ]
  • [ 204530-94-9 ]
  • [ 870774-25-7 ]
YieldReaction ConditionsOperation in experiment
67% With hydrogenchloride; n-butyllithium; In tetrahydrofuran; hexane; toluene; (8) Synthesis of Compound 2-8 Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl) naphthalene and 2.1 L of dehydrated THF was cooled down to -60 degrees C., and added with 567 mL (884.9 mmol) of hexane solution of 1.56M n-butyllithium in drops while being stirred. Then, the reaction mixture was stirred for two hours at -60 degree C. 416 g (2.21 mol) of triisopropyl borate was dropped into the reaction solution at -60 degrees C. Subsequently, the reaction mixture was stirred for 17 hours at room temperature. The reaction mixture was further added with solution of hydrochloric acid to be stirred for one hour at room temperature. After the reaction, the reaction mixture was further added with toluene, so that aqueous phase thereof was eliminated. After organic phase thereof was dried with magnesium sulfate, the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl) phenylboronic acid was obtained at an yield of 67%.
  • 3
  • [ 870774-25-7 ]
  • [ 605-02-7 ]
  • 4
  • [ 870774-25-7 ]
  • [ 1196690-48-8 ]
  • [ 1196690-50-2 ]
YieldReaction ConditionsOperation in experiment
94% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 100℃; for 18h;Inert atmosphere; Example 7; In Example 7, a synthesis method of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole (abbrev.: NPhABOx) represented by Structural Formula (131) will be described. [Step 1: Synthesis of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole] A synthesis scheme of 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole is shown in (F-1). In a 50 mL three-neck flask, 0.97 g (2.2 mmol) of 2-[4-(10-bromo-9-anthryl)phenyl]benzoxazole, 0.57 g (2.3 mmol) of 4-(1-naphthyl)phenylboronic acid, 0.46 g (4.3 mmol) of sodium carbonate, 15 mL of toluene, 3 mL of ethanol, and 3 mL of water were placed. The mixture was degassed by being stirred under reduced pressure, and the air in the flask was replaced with nitrogen. To the mixture, 35 mg (0.030 mmol) of tetrakis(triphenylphosphine)palladium(0) was added, and the mixture was stirred under nitrogen stream at 100 C. for 18 hours. After a certain period, water was added to the mixture, and an aqueous layer was extracted with toluene. The obtained extracted solution and the organic layer were combined and washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, and the organic layer was dried with magnesium sulfate. The mixture was gravity filtered, and the obtained filtrate was condensed to give a solid. The solid was purified by silica gel column chromatograghy (toluene:hexane=2:1) and recrystallized with toluene/hexane, giving 1.2 g of the target white powder in a yield of 94%. Then, 1.2 g of the target substance was subjected to sublimation purification at 385 C. under argon stream (flow rate: 3.0 mL/min) and a pressure of 10 Pa for 15 hours; thus, 1.1 g of the target substance was recovered in a yield of 91%. This compound was measured by nuclear magnetic resonance (NMR) spectrometry and identified as 2-(4-{10-[4-(1-naphthyl)phenyl]-9-anthryl}phenyl)benzoxazole (abbrev.: NPhABOx). The 1H NMR data is shown below. 1H NMR (300 MHz, CDCl3): delta (ppm)=7.38-7.47 (m, 6H), 7.55-7.78 (m, 13H), 7.84-7.99 (m, 5H), 8.17-8.20 (m, 1H), 8.53 (d, J=8.1 Hz, 2H).
  • 5
  • [ 870774-25-7 ]
  • [ 1204427-12-2 ]
  • [ 1204427-16-6 ]
YieldReaction ConditionsOperation in experiment
95% With potassium carbonate; tris-(o-tolyl)phosphine;palladium diacetate; In ethanol; water; toluene; at 80℃; for 5h;Inert atmosphere; In a 200 mL three neck flask were put 2.5 g (4.4 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.1 g (4.4 mmol) of 4-(1-naphthyl)phenylboronic acid, and 0.33 g (1.1 mmol) of tri(ortho-tolyl)phosphine. The atmosphere in the flask was replaced with nitrogen. To this mixture were added 5.0 mL of an aqueous potassium carbonate solution (2.0 mol/L), 60 mL of toluene, and 20 mL of ethanol. This mixture was stirred to be degassed while the pressure was reduced. To this mixture was added 49 mg (0.22 mmol) of palladium(II) acetate. This mixture was stirred under a nitrogen stream at 80 C. for 5 hours.After being stirred, the mixture was separated into an aqueous layer and an organic layer. The aqueous layer was extracted with toluene. The extract and the organic layer were combined and washed with saturated brine. Then, the organic layer was dried with magnesium sulfate, followed by gravity filtration of this mixture. An oily substance obtained by concentration of the resulting filtrate was dissolved in about 10 mL of toluene. This solution was suction filtered through Celite (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). An oily substance obtained by concentration of the resulting filtrate was purified by silica gel column chromatography (the developing solvent was a mixed solvent of a 5:1 ratio of hexane to toluene) to give a light yellow oily substance.This oily substance was recrystallized with a mixed solvent of toluene and hexane to give the desired substance as 2.4 g of a light yellow powder in a yield of 79%. Sublimation purification of 2.3 g of the light yellow powder obtained was performed by a train sublimation method. The light yellow powder was heated at 340 C. with an argon flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 2.2 g of a light yellow solid which was the desired substance was obtained in a yield of 95%. By a nuclear magnetic resonance (NMR) method, this compound was confirmed to be 3-[4-(1-naphthyl)phenyl]-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPAalphaNP) which was the desired compound.The following are data of the 1H NMR measurement of the compound obtained: 1H NMR (CDCl3, 300 MHz):delta=7.37-7.67 (m, 17H), 7.70-7.80 (m, 6H), 7.85-7.96 (m, 9H), 8.06 (d, J=8.1 Hz, 1H), 8.29 (d, J=7.8 Hz, 1H), 8.52 (d, J=0.90 Hz, 1H)In addition, FIGS. 18A and 18B show 1H NMR charts. Note that FIG. 18B is a chart showing an enlarged part in the range of 7.2 ppm to 8.4 ppm in FIG. 18A.
With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 5h;Inert atmosphere; Into a 200 mL three-neck flask were put 2.5 g (4.4 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.1 g (4.4 mmol) of 4-(l-naphthyl)phenylboronic acid, and 0.33 g (1.1 mmol) of tri(ortho-tolyl)phosphine , and the air in the flask was replaced with nitrogen. To this mixture were added 5.0 mL (2.0 mol/L) of a potassium carbonate aqueous solution, 60 mL of toluene, and 20 mL of ethanol. This mixture was stirred to be degassed while the pressure was reduced. To the mixture was added 49 mg (0.22 mmol) of palladium(II) acetate, and the mixture was stirred at 80 0C under a nitrogen stream for 5 hours. After the stir, the aqueous layer of the mixture was extracted with toluene and the extracted solution and the organic layer were washed together with saturated saline. After that, the organic layer was dried with magnesium sulfate, and this mixture was subjected to gravity filtration. The obtained filtrate was concentrated to give an oily substance. The obtained oily substance was dissolved in about 10 mL of toluene. This solution was subjected to suction filtration through Celite (Catalog No. 531-16855, manufactured by Wako Pure Chemical Industries, Ltd.), alumina, and Florisil (Catalog No. 540-00135, manufactured by Wako Pure Chemical Industries, Ltd.). The obtained filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane and toluene (hexane: toluene= 5: I)) to give a light yellow oily substance. The oily substance was recrystallized with a mixed solvent of toluene and hexane to give 2.4 g of light yellow powder, which was the object, at a yield of 79%[0476]Sublimation purification by train sublimation was performed on 2.3 g of the obtained light yellow powder. The sublimation purification was performed under such conditions that the light yellow powder was heated at 340 0C with an argon gas applied at a flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 2.2 g of a light yellow solid, which was the objective compound, was obtained at a yield of 95%. [0477]This compound was identified as3-[4-(l-naphthyl)phenyl]-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (CzPAaNP) which was the object by nuclear magnetic resonance (NMR). 1H NMR data of the obtained compound is shown below. 1H NMR(CDCl3, 300 MHz): d= 7.37-7.67(m, 17H), 7.70-7.80(m, 6H), 7.85-7.96(m, 9H), 8.06(d, J= 8.1 Hz, IH), 8.29(d, J= 7.8 Hz,IH), 8.52(d, J= 0.90 Hz, IH)[0478]Further, the 1H NMR chart is illustrated in FIGS. 52A and 52B. Note that FIG.52B is a chart showing an enlarged portion of FIG. 52A in the range of from 7.2 ppm to 8.4 ppm.
  • 6
  • [ 870774-25-7 ]
  • C33H19Br [ No CAS ]
  • [ 1220509-81-8 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; (2-3) Synthesis of Compound 35; 4 g of Intermediate 11, 2.3 g of 4-(l~naphthalene)-l-phenylboronic acid, 40 ml of tetrahydrofuran, 2.5 g of potassium carbonate and 20 ml of water were mixed in a 100 ml round-bottom flask with stirring. 0.53 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 2 g of the title compound. 1H-NMR(CDCl3, 500MHz) (IH, d, 8.48532, 8.46735), (IH, d, 8.41562, 8.40007), (IH, d, 8.07572, 8.05957), (2H, d, 7.99909, 7.98380), (3H, m, 7.94149-7.88387), (IH, d, 7.83335, 7.81698), (6H, m,7.71184-7.61582), (4H, m5 7.56625 -7.48845), (2H, t, 7.4.551 -7.37579), (IH, t, 7.19805 -7.16625), (IH, t, 7.15543 -7.12234), (3H, t, 7.10562, 7.07492), (2H, d, 7.02127 -7.00615), (IH, t, 6.84303 -6.81196), (IH, d, 6.62948, 6.61470) EI-MS : m/z 618(M+)
  • 7
  • [ 870774-25-7 ]
  • 3-bromo-10-phenylspiro[benzo[ij]tetraphene-7,9'-fluorene] [ No CAS ]
  • [ 1220509-86-3 ]
YieldReaction ConditionsOperation in experiment
81% With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; for 0.5h; General procedure: A solution of 3-bromo-10-phenylspiro[benzo[ij]tetraphene-7,9'-fluorene] (5.71 g, 10 mmol), tetrakis(triphenylphosphine)palladium(0) (0.59 g, 0.51 mmol), and naphthalene-1-boronic acid (1.72 g, 10 mmol) dissolved in THF (150 mL) was stirred in a double-necked flask for 30 min. Potassium carbonate (2 M, 150 mL) was added dropwise over 20 min. The resulting reaction mixture was refluxed overnight at 80C and then extracted with ethyl acetate and water. After the organic layer was evaporated with a rotary evaporator, the resulting powdery product was purified by column chromatography from dichloromethane/n-hexane (1/1) to give the yellow 1N-PSBTF crystalline product. 2N-PSBTF and NP-PSBTF were prepared using similar procedures described above.
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; (3-5) Synthesis of Compound 110; 1.6 g of Intermediate 12, 0.86 g of 4-(l -naphthalene)- 1-phenylboronic acid, 20 ml of tetrahydrofuran, 1 g of potassium carbonate and 10 ml of water were mixed in a 100 ml round-bottom flask with stirring. 0.2 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 1.5 g of the title compound. 1H-NMR(CDCl3, 500MHz) (IH, d, 8.50970-8.49168), (IH, d, 8.42353, 8.4.794), (IH, d, 8.07996, 8.06194), (2H, d, 8.01643, 8.00113), (IH, d, 7.98321, 7.96542), (3H, m, 7.94593-7.89355), (IH, d, 7.84365, 7.82718), (5H, m, 7.69204-7.61719), (6H, d, 7.58142-7.47368), (4H, m, 7.41957-7.35884), (IH, t, 7.30467-7.27303), (5H, m, 7.16011-7.09383), (2H, d, 7.05529, 7.04019), (IH, d, 6.64619, 6.63128) EI-MS : m/z 695(M+)
  • 8
  • [ 870774-25-7 ]
  • [ 1220510-00-8 ]
  • [ 1220510-02-0 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80℃; (5-6) Synthesis of Compound 260; 1O g of Intermediate 16, 4.7 g of 4-(l -naphthalene)- 1-phenylboronic acid, 100 ml of tetrahydrofuran, 3.9 g of potassium carbonate and 40 ml of water were mixed in a 100 ml round-bottom flask with stirring. 1.1 g of tetrakis(triphenylphosphine)palladium(0) was added to the mixture, which was heated to 80 C . The reaction solution was cooled and filtered, and the precipitated crystals were washed with acetone and subjected to recrystalization with methylene chloride, to obtain 12 g of the title compound. 1H-NMR(CDCl3, 500MHz) lH(d, 8.48257-8.46562), lH(d, 8.40254-8.38596), lH(d, 8.05832-8.04220), 2H(d, 8.00324-7.98666), lH(d, 7.97954-7.96394), 3H(m, 94291-7.88471), lH(d, 7.86588-7.84936), 5H(m, 7.60124-7.61055), 6H(m, 7.56555-7.48242), 4H(m, 7.44577-7.38305), lH(t, 7.31357-7.29255), 4H(7.18356-7.12363), lH(d, 7.09144-7.07529), lH(d, 6.65264-6.63775), 3H(s, 2.68341) EI-MS : m/z 709(M+)
  • 9
  • [ 870774-25-7 ]
  • [ 106-40-1 ]
  • [ 1222561-66-1 ]
YieldReaction ConditionsOperation in experiment
95% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 60 - 80℃; for 1.5h;Inert atmosphere; Step 1: Synthesis of 4'-(1-naphthyl)biphenyl-4-amine To a 50 mL three-neck flask were added 0.70 g (4 mmol) of 4-bromoaniline, 1.0 g (4 mmol) of 4-(1-naphthyl)phenylboronic acid, and 61.8 mg (0.2 mmol) of tris(o-tolyl)phosphine, and nitrogen substitution in the flask was carried out. To the mixture were added 14 mL of toluene, 6 mL of ethanol, and 4 mL of an aqueous solution of potassium carbonate (2 mol/L). The mixture was stirred to be degassed under a reduced pressure, and then the mixture was heated at 60 C., which was followed by addition of 11.9 mg (0.05 mmol) of palladium(II) acetate. This mixture was stirred at 80 C. for 1.5 hours. After the reaction, toluene and water were added to the mixture, the organic layer and the aqueous layer were separated from each other, and the aqueous layer was extracted twice with toluene. The obtained extract and the organic layer were combined, washed with brine, and dried with magnesium sulfate. The mixture was subjected to gravity filtration to remove magnesium sulfate, and the filtrate was concentrated to obtain an oily product. The oily product was subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina, resulting in a filtrate. The filtrate obtained was concentrated to give 1.1 g of an oily substance which was a target substance in 95% yield. The synthetic scheme of 4'-(1-naphthyl)biphenyl-4-amine is shown in (B-1).
  • 10
  • [ 870774-25-7 ]
  • (R)-2,6-dibromo-4H-dinaphtho[2,1-d:1',2'-f][1,3,2]dithiazepine-3,3,5,5-tetraoxide [ No CAS ]
  • C52H33NO4S2 [ No CAS ]
  • 11
  • [ 870774-25-7 ]
  • [ 1564-64-3 ]
  • [ 1092390-00-5 ]
YieldReaction ConditionsOperation in experiment
92% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; for 12h;Inert atmosphere; Reflux; d. Preparation of Intermediate IInto a RBF (5000 mL) was added 9-bromoanthracene (100 g, 0.389 mol), 4-(Naphthalene-1-yl) Phenyl boronic acid (116 g, 0.469 mol), followed by the addition of toluene (3000 mL). The mixture was purged with N2 for 10 min. Then Na2CO3 (124 g, 1.167 mole) dissolved in the water (600 mL) was added. The mixture was continued to be purged with N2 for 10 min. A catalytic amount of Pd(PPh3)4 (2.3 g, 1.95 mmole) was added. The mixture was refluxed under N2 for 12 h. Cooled down the reaction mixture to 40 C., filtered, separated off water layer, and concentrate the organic phase to a final volume (150 ml) to obtain the solid of intermediate I (131 g, yield: 92%). C30H2O: El, MS m/z (%): 380 (100, M+).
  • 12
  • [ 204530-94-9 ]
  • [ 870774-25-7 ]
YieldReaction ConditionsOperation in experiment
67% Under an argon gas atmosphere, a mixture of 208.8 g (737.4 mmol) of 1-(4-bromophenyl)naphthalene and 2.1 L of dehydrated TI-IF was cooled down to minus 60 degree C. Then, 567 ml (884.9 mmol) of hexane solution of 1.56M n-butyllithium was dropped into the mixture while the mixture was being stirred. The reaction mixture was further stirred at minus 60 degrees for 2 hours. 416 g (2.21 mol) of triisopropylborate was dropped into the reaction mixture at minus 60 degrees C. The reaction mixture was then stirred at room temperature for 17 hours. The reaction mixture was added with aqueous solution of hydrochloric acid and stirred at room temperature for 1 hour. After the reaction, the reaction mixture was added with toluene, and aqueous phase thereof was eliminated. Then, organic phase thereof was dried with magnesium sulfate, and the solvent was distilled away under reduced pressure. By recrystallizing the obtained solid by toluene, 126 g of 4-(1-naphthyl)phenylboronic acid was obtained at an yield of 67%.
  • 13
  • [ 870774-25-7 ]
  • [ 5467-58-3 ]
  • [ 1303519-13-2 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;tetrakis(triphenylphosphine)palladium (0); In tetrahydrofuran; water; toluene; 3-a. Synthesis of 1-methoxy-4-{4-(naphthalen-1-yl)phenyl}naphthalene 1-Methoxy-4-{4-(naphthalen-1-yl)phenyl} was synthesized as follows. 1-Bromo-4-methoxynaphthalene (25 g, 0.105 mol), 4-(naphthalen-1-yl)phenylboronic acid (30.4 g, 0.137 mol), potassium carbonate (21.9 g, 0.16 mol), tetrakis(triphenylphosphine)palladium(0) (2.4 g, 0.01 mol), water (25 mL), tetrahydrofuran (75 mL) and toluene (75 mL) were stirred in a 250 mL round-bottom flask for 12 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate (300 mL) and water (1000 mL). The organic layer was dried with magnesium sulfate and concentrated under reduced pressure to obtain a solid. The solid was dissolved in hot toluene (400 mL) and then filtered. The filtrate was recrystallized in methanol (800 mL). The resultant solid was filtered and washed with hexane (300 mL) to obtain a product (20 g, 0.055 mol, 52.6%).
  • 14
  • [ 38557-72-1 ]
  • [ 870774-25-7 ]
  • [ 1337916-14-9 ]
YieldReaction ConditionsOperation in experiment
50% With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In water; acetonitrile; at 50℃;Inert atmosphere; Microwave irradiation; Step 1: Synthesis of 3,5-Dimethyl-2-(4-naphthalen-1-yl-phenyl)pyrazine (abbreviation: Hdm1nppr)First, into a recovery flask equipped with a reflux pipe were placed 0.74 g of 2-chloro-3,5-dimethylpyrazine, 1.29 g of 4-(1-naphthyl)phenylboronic acid, 0.55 g of sodium carbonate, 0.024 g of bis(triphenylphosphine)palladium(II) dichloride (abbreviation: Pd(PPh3)2Cl2), 10 mL of water, and 10 mL of acetonitrile, and the air in the flask was replaced with argon. This reaction container was irradiated with microwaves (2.45 GHz, 100 W) for 15 minutes, so that heating was performed. Then, the reaction container was cooled to 50 C. or less. Water was added to the reaction solution, and the organic layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried with magnesium sulfate. The solution which had been dried was filtered. The solvent of this solution was distilled, and recrystallized using ethyl acetate, whereby Hdm1nppr, which is the pyrazine derivative to be produced, was obtained (as a white powder in 50% yield). Note that the microwave irradiation was performed using a microwave synthesis system (Discover, manufactured by CEM Corporation). The synthesis scheme of Step 1 is illustrated in the following (a-1).
  • 15
  • [ 870774-25-7 ]
  • [ 797035-61-1 ]
  • [ 1359730-64-5 ]
YieldReaction ConditionsOperation in experiment
38% Synthesis Example 1 This example illustrates the preparation of compound A1 .To a 500 ml_ round bottle flask were added 4,4'-dibromo-2,2'-dimethyl-1 ,1 '- binaphthyl (4.40 g, 10 mmol), 4-(naphthalen-1 -yl)phenylboronic acid (5.21 g, mmol), sodium carbonate (2 M, 30 ml_, 60 mmol), toluene (120 ml_) and Aliquat 336 (0.5 g). The mixture was system was stirred under nitrogen for 20 min. After which Tetrakis(triphenylphosphine) (462 mg, 0.4 mmol) was added and the mixture was stirred under nitrogen for another 15 min. The reaction was then heated in an oil bath at 95 C for 18 hour. After cooling, the mixture was filtered through a Celite pad to remove the insoluble materials. The solution was washed with diluted HCI (10%, 80 ml_), water (80 ml_) and saturated brine (50 ml_). The solvent was removed by rotary evaporation. The crude product was passed through a Silica gel column eluted with toluene. The product containing fractions were combined and the solvent was removed by rotary evaporation.Recrystallization from methylene chloride and acetonitrile gave the product as a white crystalline material. Yield, 2.6 g (38%). NMR spectra was consistent with the structure.
  • 16
  • [ 5394-23-0 ]
  • [ 870774-25-7 ]
  • [ 1233221-58-3 ]
YieldReaction ConditionsOperation in experiment
89% With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water;Reflux; Example 14; This example illustrates the preparation of phenanthroline derivative Compound 19.To 4,7-dichlorophenanthroline (1.245 g, 0.0050 mol) and the 3-boronate ester of triphenylamine (4.1 g, 0.0111 mol), Pd2/DBA3 (0.3 g) and tricyclohexyl phosphine (0.21 g) in 30 ml 1,4-dioxane was added followed by 4.75 g K3PO4 in 15 ml of water and refluxed overnight. Cooled and performed water/Chloroform extraction of mixture. recrystallized from DCM/hexanes, then silica chromatography using CHCl3/MeOH concentrated heart cuts almost all the way and filtered for 1.6 grams Yield is 89%. The structure was confirmed by NMR analysis to be Compound 19:
  • 17
  • [ 870774-25-7 ]
  • [ 1229012-68-3 ]
  • [ 1233221-49-2 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere; Example 2; Example 2 illustrates the preparation of phenanthroline derivative Compound 3, using Suzuki coupling of 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline from Example 1 with 4-(1-naphthyl)-phenylboronic acid; To 2.0 g of dichlorobathophenanthroline (5 mM) from Example 1 was added 2.6 g (11 mM) boronic acid in a glove box. To this was added 0.15 g tris(dibenzylideneacetone)dipalladium (0) (?Pd2 DBA3?) (0.15 mM), 0.1 g tricyclohexylphosphine (0.35 mM), and 3.75 g potassium phosphate (17 mM), and all were dissolved into 30 mL dioxane and 15 mL water. This was mixed and heated in a glove box at 100 C. for 1 hr, then warmed gently (minimum rheostat setting) under nitrogen overnight. On reaching about 80 C. the mixture was a tan brown slurry which slowly became clear brown with a dense precipitate. As the solution refluxed (air condensor) a white fibrous precipitate formed. This was cooled and the white fibers were filtered from the dioxane after adding additional water. The fibers were dissolved into chloroform and then evaporated and precipitated in toluene by adding methanol, as off white powder. This was collected by filtration and washed well with methanol to isolate 2.75 g of Compound 3.
  • 18
  • [ 870774-25-7 ]
  • [ 57103-20-5 ]
  • [ 1365608-78-1 ]
YieldReaction ConditionsOperation in experiment
69% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 13h;Inert atmosphere; Example 7; In this example, an example in which 3,6-bis-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: NP2PC) represented by Structural Formula (112) in Embodiment 1 is manufactured will be described. In a 200-mL three-neck flask, a mixture of 2.0 g (5.0 mmol) of 3,6-dibromo-9-phenyl-9H-carbazole, 2.7 g (11 mmol) of 4-(1-naphthyl)phenylboronic acid, 100 mg (0.5 mmol) of palladium(II) acetate, 41 mg (0.1 mmol) of tri(o-tolyl)phosphine, 20 mL of toluene, 2 mL of ethanol, and 30 mL of a potassium carbonate aqueous solution (2 mol/L) was deaerated while being stirred under reduced pressure, and then heated and stirred in a nitrogen atmosphere at 85° C. for 13 hours to be reacted.After the reaction, 150 mL of toluene was added to the reaction mixture solution, and an organic layer of the mixture solution was filtrated through Florisil, alumina, and Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to adsorb moisture. This suspension was filtrated to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and acetone and methanol were added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 2.2 g of white powder that was an objective substance in a yield of 69percent. The reaction scheme of the synthesis method is shown in (F7-1). The Rf values of the objective substance and 3,6-dibromo-9-phenyl-9H-carbazole were respectively 0.25 and 0.58 which were obtained by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate and hexane in a 1:10 ratio).The obtained compound was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.45-7.68 (m, 19H), 8.02 (dd, J=2.1 Hz, 9.0 Hz, 2H), 7.87-7.95 (m, 8H), 8.05 (d, J=7.8 Hz, 2H), 8.55 (d, J=1.5 Hz, 2H).FIGS. 26A and 26B are 1H NMR charts. Note that FIG. 26B is a chart showing an enlarged part of FIG. 26A in the range of 7.0 ppm to 9.0 ppm. The measurement results confirmed that NP2PC that was the objective substance was able to be obtained.FIG. 27A shows an absorption spectrum of NP2PC in a toluene solution of NP2PC, and FIG. 27B shows an emission spectrum thereof. FIG. 28A shows an absorption spectrum of a thin film of NP2PC, and FIG. 28B shows an emission spectrum thereof. The absorption spectrum was measured with a UV-visible spectrophotometer (V550, produced by JASCO Corporation). The emission spectrum was measured with a fluorescence spectrophotometer (FS920, produced by Hamamatsu Photonics Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. FIG. 27A show the absorption spectrum of NP2PC in the solution of NP2PC which was obtained by subtracting the absorption spectra of the quartz cell and toluene put therein, and FIG. 28A shows the absorption spectrum of the thin film which was obtained by subtracting the absorption spectrum of the quartz substrate. In FIGS. 27A and 27B and FIGS. 28A and 28B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, the absorption peak was observed at around 314 nm, and the maximum emission wavelength was 392 nm (excitation wavelength: 310 nm). In the case of the thin film, the absorption peak was observed at around 314 nm, and the maximum emission wavelength was 404 nm (excitation wavelength: 315 nm).The absorption spectrum showed that NP2PC described in this example is a material having weak absorption of light in the visible region. In addition, the emission spectrum shows that NP2PC exhibits blue-violet emission.Further, the thermophysical property was examined with a differential scanning calorimeter (DSC). The measurement result showed that the melting point is 269° C. In addition, glass transition and a crystallization peak were not observed; thus, it was found that NP2PC is a substance which is difficult to be crystallized.
  • 19
  • [ 1153-85-1 ]
  • [ 870774-25-7 ]
  • [ 1365452-27-2 ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; Synthesis Example 1; In a 200-mL three-neck flask, a mixture of 5.0 g (15.5 mmol) of 3-bromo-9-phenyl-9H-carbazole, 4.2 g (17.1 mmol) of 4-(1-naphthyl)-phenylboronic acid, 38.4 mg (0.2 mmol) of palladium(II) acetate, 104 mg (0.3 mmol) of tris(2-methylphenyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 mL of a potassium carbonate aqueous solution (2 mol/L) was deaerated while being stirred under reduced pressure, and then heated and stirred in a nitrogen atmosphere at 85 C. for 9 hours to be reacted.After the reaction, 500 mL of toluene was added to the reaction mixture solution, and an organic layer of the mixture solution was filtrated through Florisil (Catalog No. 540-00135, produced by Wako Pure Chemical Industries, Ltd.), alumina (neutral, produced by Merck Ltd), and Celite (Catalog No. 531-16855, produced by Wako Pure Chemical Industries, Ltd.). The obtained filtrate was washed with water, and magnesium sulfate was added thereto so that moisture was adsorbed. This suspension was filtrated to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.24 g of white powder that was an objective substance in a yield of 90%. The reaction scheme of Synthesis Example 1 above is shown in (F1-1). The Rf values of the objective substance and 3-bromo-9-phenyl-9H-carbazole were respectively 0.42 and 0.58, which were obtained by silica gel thin layer chromatography (TLC) (with a developing solvent of ethyl acetate and hexane in a 1:10 ratio).The compound obtained in Synthesis Example 1 was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.30-7.35 (m, 1H), 7.44-7.67 (m, 14H), 7.76 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.84-7.95 (m, 4H), 8.04 (d, J=7.8, 1H), 8.23 (d, J=7.8, 1H), 8.46 (d, J=1.5, 1H).FIGS. 7A and 7B are 1H NMR charts. Note that FIG. 7B is a chart showing an enlarged part of FIG. 7A in the range of 7.0 ppm to 9.0 ppm. The measurement results confirmed that 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN) that was the objective substance was able to be obtained.
90% With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; In a 200 mL three-neck flask, a mixture of 5.0 g (15.5 mmol) of 3-bromo-9-phenyl-9H-carbazole, 4.2 g (17.1 mmol) of 4-(1-naphthyl)-phenylboronic acid, 38.4 mg (0.2 mmol) of palladium(II) acetate, 104 mg (0.3 mmol) of tri(ortho-tolyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 mL of a 2 mol/L aqueous potassium carbonate solution was degassed while being stirred under reduced pressure, and reacted by being stirred and heated at 85 C. for 9 hours under a nitrogen atmosphere. (0523) After the reaction, 500 mL of toluene was added to this reaction mixture solution, and the organic layer of this mixture solution was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The obtained filtrate was washed with water, and magnesium sulfate was added thereto so that moisture was adsorbed. This suspension was filtered to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 6.24 g of a white powder in a yield of 90%, which was the object of the synthesis. (0524) This compound was identified as 3-[4-(1-naphthyl)-phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN), which was the object of the synthesis, by nuclear magnetic resonance (1H-NMR) spectroscopy. (0525) 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.30-7.35 (m, 1H), 7.44-7.67 (m, 14H), 7.76 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.84-7.95 (m, 4H), 8.04 (d, J=7.8, 1H), 8.23 (d, J=7.8, 1H), 8.46 (d, J=1.5, 1H).
90% With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 85℃; for 9h;Inert atmosphere; In a 200 mL three-necked flask3-bromo-9-phenyl-9H-carbazole(11.5 mmol) of 4- (1-naphthalene) phenylboronic acid, 38.4 mg (0.2 mmol) of palladium (II) acetate, 104 mg (0.3 mmol) of tris (o-tolyl) , 50 mL of toluene, 5 mL of ethanol and 2 ml of a 20 mol / L aqueous solution of potassium carbonate were degassed with stirring under reduced pressure, and then stirred at 85 C for 9 hours under nitrogen atmosphere to cause reaction.After the reaction, 500 mL of toluene was added to the reaction mixture, and the organic layer of the mixed solution was treated with magnesium silicate (Japan Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), alumina and diatomaceous earth (Manufactured by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855). The resulting filtrate was washed with water and magnesium sulfate was added to adsorb moisture. The suspension was filtered to obtain a filtrate. The resulting filtrate was concentrated and then purified by silica gel column chromatography. In this case, as a developing solvent for silica gel column chromatography, a mixed solvent of toluene and hexane (toluene: hexane = 1: 4) was used. The resulting rinsing was concentrated, and methanol was added and ultrasonic waves were applied, followed by recrystallization, and a white powder of the desired product was obtained at a yield of 6.24 g and a yield of 90%.
  • 20
  • [ 870774-25-7 ]
  • [ 934545-83-2 ]
  • [ 1369431-26-4 ]
YieldReaction ConditionsOperation in experiment
82% With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 100℃; for 7h;Inert atmosphere; Step 2: Synthesis Method of 9-(1-naphthyl)-3-[4-(1-naphthyl)-phenyl]-9H-carbazole (abbreviation: NCPN)In a 200-mL three-neck flask, a mixture of 5.0 g (13 mmol) of 3-bromo-9-(1-naphthyl)-9H-carbazole, 3.7 g (15 mmol) of 4-(1-naphthyl)phenylboronic acid, 34 mg (0.2 mmol) of palladium(II) acetate, 91 mg (0.3 mmol) of tris(2-methylphenyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 30 mL of a potassium carbonate aqueous solution (2 mol/L) was deaerated while being stirred under reduced pressure, and then heated and stirred in a nitrogen atmosphere at 100 C. for 1 hour to be reacted. Furthermore, 334 mg (1.35 mmol) of 4-(1-naphthyl)phenylboronic acid, 15.0 mg (0.07 mmol) of palladium(II) acetate, and 45 mg (0.15 mmol) of tris(2-methylphenyl)phosphine were added, and the mixture was heated and stirred in a nitrogen atmosphere at 100 C. for 6 hours to be reacted.After the reaction, 500 mL of toluene was added to the reaction mixture solution, and an organic layer of the mixture solution was filtrated through Florisil, alumina, and Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to adsorb moisture. This suspension was filtrated to obtain a filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At this time, a mixed solvent of toluene and hexane (toluene:hexane=1:4) was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and hexane was added thereto. The mixture was irradiated with ultrasonic waves and then recrystallized to give 5.4 g of white powder that was an objective substance in a yield of 82%. The reaction scheme of Step 2 is shown in (F6-2). The Rf values of the objective substance and 3-bromo-9-(1-naphthyl)-9H-carbazole were respectively 0.25 and 0.53 which were obtained by silica gel thin layer chromatography (TLC) (with a developing solvent containing ethyl acetate and hexane in a 1:10 ratio).The obtained compound was examined by a nuclear magnetic resonance (NMR) method. The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta (ppm)=7.04 (dd, J=6.3 Hz, 1.5 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H), 7.30-7.70 (m, 14H), 7.83-7.94 (m, 4H), 8.02-8.07 (m, 3H), 8.28 (dd, J=6.3 Hz, 2.4 Hz, 1H), 8.52 (d, J=1.5 Hz, 1H).FIGS. 23A and 23B are 1H NMR charts. Note that FIG. 23B is a chart showing an enlarged part of FIG. 23A in the range of 6.0 ppm to 9.0 ppm. The measurement results confirmed that NCPN that was the objective substance was able to be obtained.FIG. 24A shows an absorption spectrum of NCPN in a toluene solution of NCPN, and FIG. 24B shows an emission spectrum thereof. FIG. 25A shows an absorption spectrum of a thin film of NCPN, and FIG. 25B shows an emission spectrum thereof. The absorption spectrum was measured with a UV-visible spectrophotometer (V550, produced by JASCO Corporation). The emission spectrum was measured with a fluorescence spectrophotometer (FS920, produced by Hamamatsu Photonics Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. FIG. 24A show the absorption spectrum of NCPN in the solution of NCPN which was obtained by subtracting the absorption spectra of the quartz cell and toluene put therein, and FIG. 25A shows the absorption spectrum of the thin film which was obtained by subtracting the absorption spectrum of the quartz substrate. In FIGS. 24A and 24B and FIGS. 25A and 25B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, the absorption peak was observed at around 300 nm, and the maximum emission wavelength was 388 nm (excitation wavelength: 300 nm). In the case of the thin film, the absorption peak was observed at around 322 nm, and the maximum emission wavelength was 397 nm (excitation wavelength: 328 nm).The absorption spectrum showed that NCPN described in this example is a material having weak absorption of light in the visible region. In addition, the emission spectrum shows that NCPN exhibits blue-violet emission.
  • 21
  • [ 870774-25-7 ]
  • [ 292638-85-8 ]
  • (E)-methyl 3-(4-(naphthalen-1-yl)phenyl)acrylate [ No CAS ]
  • 22
  • [ 870774-25-7 ]
  • [ 853945-50-3 ]
  • 23
  • [ 870774-25-7 ]
  • [ 523-27-3 ]
  • [ 1092390-01-6 ]
YieldReaction ConditionsOperation in experiment
97.5% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 1.5h;Inert atmosphere; Reflux; In a 1000ml three-necked flask, with mechanical stirring, Ar gas protection, 11.7g of 9,10-dibromoanthracene (molecular weight(0.35, 0.035 mol), 8.7 g of 4- (1-naphthyl) benzeneboronic acid (molecular weight: 248,0.035 mol), and Pd (PPh3)1.8 g (molecular weight 1154, 0.001556 mol), 120 ml (2M) of sodium carbonate aqueous solution, 250 ml of toluene and 150 ml of ethanol. The mixture was stirred and refluxed, and the reaction was monitored by TLC. The reaction was complete after 1.5 hrs of reaction. Cooled, separated, evaporated to dryness, the product was isolated by column chromatography, drenchedLotion with 1: 5 ethyl acetate: petroleum ether gave 15.8 g of a white solid9- (4- (1-naphthyl) phenyl) -10-bromoanthracene (AN1), product molecular weight 458, purity 98.7%, yield: 97.5%.
9,10-Dibromoanthracene (10 g, 0.03 mol), tetrakis(triphenylphosphine)palladium(0) (1.72 g, 1.49 mmol) and <strong>[870774-25-7]4-(naphthalene-1-yl)phenylboronic acid</strong> (7.4 g, 0.03 mol) were dissolved in THF (350 mL) in a double-necked flask and stirred for 30 min. Then, potassium carbonate (2 M, 200 mL) was added dropwise over 20 min. The mixture was degassed and refluxed overnight at 80 C under a nitrogen atmosphere. After being cooled, the solvent was evaporated under vacuum, and the product was extracted with ethyl acetate and water. The ethyl acetate solution was washed with water and dried with MgSO4. Evaporation of the solvent, followed by column chromatography using n-hexane on a silica gel, yielded a white yellow product
  • 24
  • [ 870774-25-7 ]
  • [ 1268515-14-5 ]
  • [ 1268514-56-2 ]
  • 25
  • [ 870774-25-7 ]
  • [ 1564-64-3 ]
  • [ 1092390-01-6 ]
  • 26
  • [ 870774-25-7 ]
  • [ 71730-46-6 ]
  • (4R)-4-(1-naphthyl)-3,4-dihydro-1,2,3-benzoxathiazine-2,2-dioxide [ No CAS ]
  • 27
  • [ 870774-25-7 ]
  • [ 14790-72-8 ]
  • (2E,6E)-4,4,7,11-tetramethyl-10-(naphthalen-1-yl)cycloundeca-2,6-dienone [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With acetylacetonato(1,5-cyclooctadiene)rhodium(I); In 1,4-dioxane; water; at 100℃; for 24h;Schlenk technique; Inert atmosphere; General procedure: Zerumbone (1) (1 equiv), boronic acid 2a (2 equiv) and [Rh(acac)(cod)] (10 mol %) were added to a Schlenk tube and the contents degassed. The mixture was dissolved in 1,4-dioxane-H2O (3:1, 2 mL) and stirred at 100 C for 12-24 h under an Ar atm. After completion of the reaction (as indicated by TLC analysis), the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography (EtOAc-hexane) to afford the product.
  • 28
  • [ 870774-25-7 ]
  • [ 1202564-31-5 ]
  • 2-[4-(naphthalen-1-yl)phenyl]dibenzo[f,h]quinoxaline [ No CAS ]
YieldReaction ConditionsOperation in experiment
69% With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 12h;Inert atmosphere; This example shows a method of synthesizing 2-[4-(naphthalen-1-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: NPDBq) represented by the following structural formula (101). In a 200 mL three-neck flask, a mixture of 2.7 g (10 mmol) of 2-chlorodibenzo[f,h]quinoxaline, 2.7 g (11 mmol) of 4-(1-naphthyl)phenylboronic acid, 23 mg (0.1 mmol) of palladium(II) acetate, 91 mg (0.3 mmol) of tri(ortho-tolyl)phosphine, 43 mL of toluene, 4 mL of ethanol, and 14 mL of an aqueous solution of potassium carbonate (2 mol/L) was degassed while being stirred under reduced pressure, and was then reacted by being heated and stirred under a nitrogen atmosphere at 80 C. for 12 hours. After the reaction, 500 mL of toluene was added to this reaction mixture solution, and an organic layer of the mixture solution was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina (produced by Merck & Co., Inc., neutral), and Celite (produced by Wako Pure Chemical Industries, Ltd., catalog No. 531-16855). The obtained filtrate was washed with water, and magnesium sulfate was added thereto so that moisture was adsorbed. This suspension was filtered to obtain a filtrate. The resulting filtrate was concentrated, followed by purification using silica gel column chromatography. At this time, a mixed solvent of toluene and hexane in a ratio of 1:5 was used as a developing solvent for the chromatography. The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with supersonic and then recrystallized, so that the objective substance was obtained as 3.0 g of yellow powder in a yield of 69%. The Rf values of the objective substance and 2-chlorodibenzo[f,h]quinoxaline were respectively 0.33 and 0.55, which were found by silica gel thin layer chromatography (TLC) (with a developing solvent of ethyl acetate and hexane in a ratio of 1:10). A nuclear magnetic resonance (NMR) method identified this compound as 2-[4-(naphthalen-1-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: NPDBq), which was the objective substance. 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): delta (ppm)=7.47-7.62 (m, 4H), 7.75-8.03 (m, 9H), 8.50 (d, J=8.3 Hz, 2H), 8.68 (d, J=7.3 Hz, 2H), 9.27 (d, J=7.8 Hz, 1H), 9.46-9.50 (m, 2H). The 1H NMR chart is shown in FIGS. 10A and 10B. Note that FIG. 10B is a chart showing an enlarged part of FIG. 10A in the range of 7.00 ppm to 9.60 ppm. Further, FIG. 11A shows an absorption spectrum of a toluene solution of NPDBq, and FIG. 11B shows an emission spectrum thereof. In addition, FIG. 12A shows the absorption spectrum of a thin film of NPDBq, and FIG. 12B shows the emission spectrum thereof. The measurement of the absorption spectrum was conducted by using a UV-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell and the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from the spectrum of the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from the spectrum of the thin film. In FIGS. 11A and 11B and FIGS. 12A and 12B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, an absorption peak was observed at around 377 nm, and an emission wavelength peak was 398 nm. In the case of the thin film, an absorption peak was observed at around 385 nm, and emission wavelength peaks were 429 nm, 445 nm, and 488 nm (at an excitation wavelength of 378 nm). Electrochemical characteristics of a thin film of NPDBq were measured (the measuring instrument was AC-2 produced by Riken Keiki, Co., Ltd.). Note that the measurement of electrochemical characteristics of the thin film was carried out as follows. The value of the HOMO level was obtained by conversion of the value of the ionization potential measured with a photoelectron spectrometer (AC-2, produced by Riken Keiki Co., Ltd.) in the air into a negative value. The value of the LUMO level was obtained in such a manner that the absorption edge, which was obtained from Tauc plot with an assumption of direct transition using data on the absorption spectrum of the thin film, was regarded as an optical energy gap and was added to the value of the HOMO level. From the results of the measurement of electrochemical characteristics of the thin film, the HOMO level, the LUMO level, and the band gap (Bg) were found to be -5.84 eV, -2.78 eV, and 3.06 eV, respectively. The above results reveal that NPDBq has a relatively deep HOMO level, a relatively shallow LUMO level, and a relatively wide Bg. Electrochemical characteristics of an NPDBq solution were also measured. As a measuring...
  • 29
  • [ 870774-25-7 ]
  • 7-(10-(naphthalen-1-yl)anthracen-9-yl)naphthalen-2-yl trifluoromethane sulfonate [ No CAS ]
  • 9-(naphthalene-1-yl)-10-(7-(naphthalene-1-yl)phenyl)naphthalene-2-yl anthracene [ No CAS ]
YieldReaction ConditionsOperation in experiment
2.6g With potassium phosphate; bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine; In ethanol; water; toluene; for 6.5h;Inert atmosphere; Reflux; Under the nitrogen atmosphere, 7-(10-(naphthalen-1-yl)anthracen-9-yl)naphthalen-2-yl trifluoromethane sulfonate (3.0 g) as the fifth intermediate compound, <strong>[870774-25-7](4-(naphthalen-1-yl)phenyl)boronic acid</strong> (1.9 g), bis(dibenzylideneacetone)palladium (0) (Pd(dba)2) (0.03 g), tricyclohexyl phosphine (0.03 g), potassium phosphate (2.2 g) and a mixture solvent (22 ml) of toluene, ethanol, and water (toluene/ethanol/water = 9/1/1 (volume ratio)) were added to a flask and refluxed for 6.5 hours. Once the heating is completed, the reaction solution was cooled to room temperature and added with methanol. The precipitates were collected by suction filtration. The obtained solid was washed with water followed by methanol, and washed further with ethyl acetate. The obtained crude product was dissolved in toluene, and colored components were removed by passing through a silica gel short column. The solvent was distilled off under reduced pressure. The obtained oily phase substance was added with ethyl acetate and the precipitated products were collected by suction filtration to give 9-(naphthalen-1-yl)-10-(7-(naphthalen-1-yl)phenyl)naphthalen-2-yl)anthracene (2.6 g) as the target compound represented by Formula (1-21). The scheme is illustrated in the following 'Reaction 9'. According to NMR measurement, structure of the target compound (1-21) was determined. 1H-NMR (CDCl3) : delta = 8.24 (d, 1H), 8.12-8.19 (m, 3H), 8.09 (d, 1H), 8.03 (m, 2H), 7.99 (dd, 1H), 7.88-7.96 (m, 4H), 7.83 (d, 2H), 7.64-7.76 (m, 4H), 7.62 (d, 1H), 7.46-7.59 (m, 7H), 7.31-7.35 (m, 2H), 7.20-7.28 (m, 4H).
  • 30
  • [ 870774-25-7 ]
  • [ 7559-36-6 ]
  • (R)-1-(2-nitro-1-p-tolylethyl)naphthalene [ No CAS ]
  • 31
  • [ 870774-25-7 ]
  • [ 402-43-7 ]
  • C23H15F3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With potassium phosphate; [5-(3-butylbenzimidazol-2-yliden-1-yl)-25,26,27,28-tetrapropyloxy calix[4]arene] (pyridine) palladium(II) dibromide; In 1,4-dioxane; at 100℃; for 24h;Inert atmosphere; General procedure: In air, potassium phosphate (3mmol, 0.636g), catalyst 1 (0.08mol%, 0.0009g) and arylboronic acid (2mmol) were weighed into a 50mL glass vial that was sealed with a septum and purged with N2 (3×). Dioxane (1mL) was then injected via syringe followed by the aryl bromide (1mmol) (if liquid). If the aryl bromide was a solid, it was introduced into the vial prior to purging with N2. At this time, the reaction stirred for 24h at 100C. The reaction mixture was concentrated in vacuo and directly purified via silica gel flash chromatography.
  • 32
  • [ 870774-25-7 ]
  • [ 1430055-43-8 ]
  • [ 1430055-48-3 ]
YieldReaction ConditionsOperation in experiment
84.2% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 4.5h;Inert atmosphere; Reflux; The 4,6-dibromo-2-{4-(pyridin-3-yl)phenyl}-2H-benzotriazole synthesized in Example 7 1,5 g, 4-(Naphthalen-1-yl)phenylboronic acid 2.2 g, 2M Potassium carbonate aqueous solution 5.3 ml, Toluene 30 ml, Ethanol 6 ml, and Tetrakistriphenylphosphine palladium (0) 0.1 g, were put into the reaction vessel purged with nitrogen, and were heated and refluxed for 4.5 hours with stirring. [0143] The organic layer was picked up by the separating operation, concentrated under a reduced pressure and was refined by the column chromatography to obtain 2.0 g of a yellow powder of 4,6-bis{4-(naphthalen-1-yl)phenyl}-2-{4-(pyridin-3-yl)phenyl}-2H-benzotriazole (compound 66) (yield, 84.2%). [0144] The obtained yellow powder was identified for its structure by the NMR. Fig. 12 shows the results of the 1H-NMR measurement. [0145] The following 32 signals of hydrogen were detected by the 1H-NMR (CDCl3). delta (ppm) = 8.62 (1H) 8.61 (1H) 8.36 (2H) 8.22 (1H) 8.11 (1H) 8.08 (1H) 8.02 (1H) 7.96 - 7.83 (8H) 7.81 (2H) 7.75 (2H) 7.68 (2H) 7.59 - 7.49 (10H)
  • 33
  • [ 870774-25-7 ]
  • 4-bromo-N-cyclohexyl-N-(p-tolyl)aniline [ No CAS ]
  • C35H33N [ No CAS ]
  • 34
  • [ 870774-25-7 ]
  • N<SUP>1</SUP>,N<SUP>4</SUP>-bis(4-bromophenyl)-N<SUP>1</SUP>,N<SUP>4</SUP>-di-p-tolylcyclohexane-1,4-diamine [ No CAS ]
  • C48H43BrN2 [ No CAS ]
  • 35
  • [ 870774-25-7 ]
  • [ 2766-43-0 ]
  • methyl N-(tert-butoxycarbonyl)-O-(4-(naphthalen-1-yl)phenyl)-L-serinate [ No CAS ]
 

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