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Chemical Structure| 19111-87-6 Chemical Structure| 19111-87-6

Structure of 19111-87-6

Chemical Structure| 19111-87-6

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Product Details of [ 19111-87-6 ]

CAS No. :19111-87-6
Formula : C18H11Br
M.W : 307.18
SMILES Code : BrC1=CC=C2C3=CC=CC=C3C4=CC=CC=C4C2=C1
MDL No. :MFCD16659043
InChI Key :GEDOYYDMCZUHNW-UHFFFAOYSA-N
Pubchem ID :18381174

Safety of [ 19111-87-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338

Computational Chemistry of [ 19111-87-6 ] Show Less

Physicochemical Properties

Num. heavy atoms 19
Num. arom. heavy atoms 18
Fraction Csp3 0.0
Num. rotatable bonds 0
Num. H-bond acceptors 0.0
Num. H-bond donors 0.0
Molar Refractivity 86.66
TPSA ?

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

0.0 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

3.07
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

5.57
Log Po/w (WLOGP)?

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

5.91
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.

5.67
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

5.73
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

5.19

Water Solubility

Log S (ESOL):?

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

-5.95
Solubility 0.000341 mg/ml ; 0.00000111 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.

-5.33
Solubility 0.00143 mg/ml ; 0.00000466 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

-8.26
Solubility 0.00000168 mg/ml ; 0.0000000055 mol/l
Class?

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

Poorly soluble

Pharmacokinetics

GI absorption?

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

Low
BBB permeant?

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

No
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

Yes
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

No
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.

-4.22 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

1.0
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

1.0
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

2.0
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<1.0
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)

1.66

Application In Synthesis of [ 19111-87-6 ]

* 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 [ 19111-87-6 ]

[ 19111-87-6 ] Synthesis Path-Downstream   1~6

  • 1
  • [ 19111-87-6 ]
  • [ 73183-34-3 ]
  • [ 890042-13-4 ]
YieldReaction ConditionsOperation in experiment
98% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; Inthe nitrogen ambient, after 2- bromo triphenylene (2-bromotriphenylene) 100g(326 mmol) was melted in the dimethylformamide (dimethylformamide, DMF) 1L herethe bis (pinacolrato) diboron (bis(pinacolato)diboron) 99.2 g (391 mmol),(1,1'- bis (diphenyl phosphine) dichloropalladium (II)((1,1'-bis(diphenylphosphine)ferrocene) dichloropalladium (II)) 2.66 g (3.26mmol) and potassium acetate (potassium acetate) 80 g (815 mmol) were put and150 heated for 5 hours and itrefluxed. After water was put in into the reaction solution after the reactioncompletion and the mixture was filtered it dried in the vacuum oven. Theresidue obtained in this way was refined to the flash column chromatography afterdividing and the compound I-1 113 g (98 %) was obtained.
98% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; It was dissolved 2-bromo-triphenylene (2-bromotriphenylene) 100g (326 mmol) in dimethylformamide (dimethylformamide, DMF) in a nitrogen environment 1L, where the bis (pinacolato) diboron (bis (pinacolato) diboron ) 99.2 g (391 mmol) and (1, 1 '- bis (diphenylphosphine) dichloropalladium (II) ((1, 1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II)) 2.66 g (3.26 mmol) and potassium acetate (potassium acetate) 80 put g (815 mmol) was heated to reflux for 5 hours at 150 . after the reaction was completed. Add water to the reaction mixture, filter the mixture, and dried in a vacuum oven. the obtained residue was flash column chromatography (flash column chromatography) separation and purification to give the compound I-1 113 g (98%)
98% With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; In a nitrogen atmosphere, 100 g (326 mmol) of 2-bromotriphenylene was dissolved in dimethylformamide(Pinacolato diboron) 99.2 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1,000 mL of dimethylformamide (DMF)G (391 mmol) and 1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (1,1-Bis (diphenylphosphine) ferrocene) dichloropalladium (II)) 2.66 g (3.26 mmol) and potassium acetate 80 g (815 mmol) of potassium acetate were added and the mixture was refluxed by heating at 150 DEG C for 5 hours. After completing the reaction,Water was added to the solution, the mixture was filtered, and then dried in a vacuum oven. The thus obtained residue was purified by flash column chromatographyTo obtain 113 g (98%) of the compound I-1. HRMS (70 eV, EI +): m / z Calcd for C24H23BO2: 354.1791, found
98% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; for 5h;Inert atmosphere; Reflux; In a nitrogen environment,100 g (326 mmol) of 2-bromo-trisbenzene (TCI) was dissolved in 1 L of dimethyl formamide (DMF)To this was added 99.2 g (391 mmol)Bis (pinacolato) diboron(Sigma - Aldrich Co., Ltd.),2.66 g (3.26 mmol) of (1,1'-bis (diphenylphosphino) dichloropalladium (II) and 80 g (815 mmol) of potassium acetate,And the mixture was heated and allowed to reflux at 150 C for 5 hours.When the reaction is complete,Water was added to the reaction solution,And the mixture is filtered and dried in a vacuum oven.The residue obtained is purified by column chromatography,113 g (98%) of compound I-1 were obtained.
98% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; 100 g (326 mmol) of 2-bromotriphenylene was dissolved in 1 L of dimethylformamide (DMF) under a nitrogen condition, and 99.2 g (391 mmol) of bis(pinacolato)diboron, 2.66 g (3.26 mmol) of (1,1′-bis(diphenylphosphine)ferrocene)dichloropalladium (II), and 80 g (815 mmol) of potassium acetate were added thereto. The mixed solution was refluxed by heating at a temperature of 150 C. for 5 hours. After the reaction was completed, water was added to the reaction solution. The mixture of the resulting reaction solution was then filtered, and dried in a vacuum oven. The residue obtained therefrom was separated and purified by flash column chromatography to obtain 113 g (98%) of Compound 1-1. (0435) HRMS (70 eV, EI+): m/z calcd for C24H23BO2: 354.1791, found: 354. (0436) Elemental Analysis: C, 81%; H, 7%
91% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100 - 110℃; for 5h;Inert atmosphere; Flask for 2-bromo-triphenylene (2-bromotriphenylene) 20 g (65.11 mmol), PIN2B2 19.8g (78.13mmol), Pd (dppf) Cl2 2.66g (3.26mmol), KOAc 11.5g (117.2mmol) and Dioxane put 180 mL steps was refluxed for 5 hours at 100 ~ 110oC under nitrogen. Lower the temperature to room temperature, the solvent was removed by distillation under reduced pressure. Purification of the resulting compound by silica gel column chromatography to give compound (Intermediate 20) as a pale yellow solid 20.9 g (yield: 91.0%) was obtained.
84% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; for 12h;Reflux; 2000mL 3-neck round bottom flask was added 2-bromo-triphenylene (70g, 0.283mol), bis (pinacolato) diboron (73.4g, 0.289mol), 1,4- dioxane (1000mL), 1,1 '-bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex a mixture (4.6g, 0.0057mol) and potassium acetate (55.6g, 0.566mol) and heated to reflux for 12 hours. After cooling the precipitated solid was filtered under reduced pressure and then the acid clay treatment, and was filtered through Celite. And by using the resulting filtrate was concentrated under reduced pressure The resulting solid was suspended in hexane, filtered and washed with hexane again, the white solid compound was obtained a (70g, 84% yield).
80% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; 2-bromotriphenylene (10g, 32.6mmol), bis(pinacolato) diborate (9.9g, 39.1mmol), [1,10-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.5g, 0.7mmol), and potassium acetate (16.2g, 162.8mmol) were dissolved in anhydrous 1,4-dioxane (180ml) and refluxed under nitrogen for 24h. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1) eluent to afford ( 1) a white solid, yield 80%. 1H NMR (400MHz, CDCl3) 9.15 (s, 1H), 8.84-8.82 (m, 1H), 8.71-8.64 (m, 4H), 8.07-8.05 (d, J=8.0Hz, 1H), 7.70-7.66 (m, 4H), 1.43 (s, 12H) ppm.
75% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 130℃; for 5h;Inert atmosphere; Under a nitrogen stream 3,1 g (10.0 mmol) of 2-bromotriphenylene, 3.1 g (12.0 mmol) of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane) 0.3 g (5 mol%) of Pd (dppf) cl 2, KOAc, 3.0 g (30.0 mmol) and 100 ml of 1,4-dioxane were placed and stirred at 130 C for 5 hours. The solvent of the organic layer was removed, and the residue was purified by column chromatography to obtain the desired compound A13 (2.7 g, 7.5 mmol, yield 75%).
68.6% With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 100℃; for 4h;Inert atmosphere; (2) Synthesis of Compound d-4; A nitrogen atmosphere was established in a 300-ml three-necked flask. After that, the following reagents and solvent were loaded into the flask.Compound d-2 : 11.5 g (37.4 mmol)Compound d-3: 11.4 g (44.9 mmol)Potassium acetate: 6.61 g (67.4 mmol)Dioxane: 100 ml[0094] Next, the reaction solution was stirred at roomtemperature under a nitrogen atmosphere, and to the stirred solution were added 1.53 g (1.87 mmol) of a bis (diphenylphosphino) ferrocene palladium ( II )dichloride dichloromethane adduct . The reaction solution was then warmed to a temperature of 100 C and stirred at the same temperature (100C) for 4 hours. After the completion of the reaction, the solvent in the reaction solution was evaporated under reduced pressure to give a crude product. Next, the resultant crude product was purified by silica gel column chromatography (developing solvent: chloroform-heptane mixed solvent) to afford 10.42 g of Compound d-4 as a white solid (yield: 68.6%).
With potassium acetate;Pd(dppf)2Cl2; In dimethyl sulfoxide; at 20 - 80℃; for 12h; [0098] 20.0 g of the bromotriphenylene mixture which contains about 70% of 2- bromotriphenylene based on HPLC monitored at 254nm, 18.7 g (73 mmol) of bis(pinacolato)diboron, 1.6 g of Pd(dppf)2Ci2, 20 g (200 mmol) of potassium acetate, and 400 Ml of DMSO was mixed at room temperature under N2. The mixture was degassed then heated up to 8O0C for 12 hours. After cooling to room temperature, the mixture was poured into ice water. The precipitate was then collected by filtration. The solid was dissolved in dichloromethane and dried over magnesium sulfate. The crude product was purified by column using a mixture of hexanes and dichloromethane (from 6:1 to 3:1) as eluent. 10 g of the pure product, 4,4,5,5- tetramethyl-2-(triphenylen-2-yl)-l ,3,2-dioxaborolane, was isolated.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 24h; General procedure: S-2 (1 eq.) in 1,4-dioxane 300 mL, after it was added 2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxaspiro[4.4]nonane (2 eq.), PdCl2(dppf ) (0.05eq.), into the KOAc (3 eq.) was stirred for 24 hours at 80C . After the reaction was completed the mixture was extracted with dichloromethane and H2O. After extraction and purification separated by column chromatography to give the S-1.
20.8 g With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl-formamide; for 5h;Inert atmosphere; Reflux; 20 g of 2-bromotriphenylene, 20 g of potassium acetate and 22.1 g of pinacoledboron were added to 200 ml of DMF, and the mixture was stirred under a nitrogen atmosphere. To this solution was added 4 g of palladium tetrakis triphenylphosphine and the mixture was slowly heated. Reflux was started and reflux reaction was carried out for 5 hours to confirm that the raw material disappeared by TLC analysis and the reaction was completed.The DMF solvent was distilled under reduced pressure, cooled to room temperature, dissolved in 200 ml of ethyl acetate, and washed three times with 100 ml of water to separate layers. Anhydrous magnesium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration. The organic layer was short-lined with silica gel, washed thoroughly with ethyl acetate, and concentrated under reduced pressure.60 ml of dichloromethane and 120 ml of methanol were added to the concentrate, and the mixture was refluxed for 1 hour. The mixture was cooled to room temperature. The resulting pale cream solid was filtered, washed with methanol, and hot-air dried at 80 to obtain 20.8 g of 2-triphenyleneboronic acid pinacol ester Gas chromatographic analysis was obtained at 98.6% purity.

  • 2
  • [ 121-43-7 ]
  • [ 19111-87-6 ]
  • [ 654664-63-8 ]
YieldReaction ConditionsOperation in experiment
57% The intermediates in argon atmosphere (E1) (2.90g, 9 . 44mmol), tetrahydrofuran (80 ml) mixing, cooling to -78 C. Furthermore, by adding n-BuLi (1.60M hexane solution, 6.20 ml, 9 . 91mmol), with 2-hour heating to 0 C. Then again cooling to -78 C, adding trimethoxyborane (2.58g, 24 . 8mmol), at -78 C stirring 20 minutes, with 8 hours warming to room temperature. After the reaction, adding hydrochloric acid aqueous solution (1M, 20 ml), stirring at room temperature 1 hour, extraction with ethyl acetate. The solution after drying with magnesium sulfate, concentrated, in hexane is suspended in the washing, filtering and recycling, got the midbody (E2) (1.46g, 5 . 38mmol, yield 57%).
57% Under an argon atmosphere the intermediate (A2) (2.90g, 9.44mmol), tetrahydrofuran (80mL) were mixed and cooled to -78 deg C. Then, added a solution of n-butyllithium (1.60M in hexanes, 6.20mL, 9.91mmol), 2 hours with heating until it is 0 deg C. Then cooled again to -78 deg.] C, then was added trimethoxy borane (2.58g, 24.8mmol), stirred for 20 minutes at -78 deg.] C after 8 hours with heating until it is room temperature.After completion of the reaction, aqueous hydrochloric acid (1M, 20mL), stirred at room temperature for 1 hour, extracted with ethyl acetate.The solution was dried over magnesium sulfate, concentrated, suspended in hexanes and washed, recovered by filtration, to give intermediate (A3)(1.46g, 5.38mmol, 57% yield)
Preparation of Compound (118)In tetrahydrofuran (280 mL), 1-bromotriphenylene (Compound 117) (10.6 g, 34.5 mmol) was dissolved under nitrogen atmosphere, and n-BuLi (2.5 M in n-hexane) (17.9 mL, 44.9 mmol) was slowly added dropwise thereto at -78 C. After stirring for 1 hour, trimethyl borate (7.2 g, 69 mmol) was added at low temperature, and the mixture was stirred while slowly raising the temperature to 25 C. After stirring for 16 hours, 10 M hydrochloric acid (30 mL) was added thereto. The resultant mixture was stirred for 1 hour, extracted with ethyl acetate (200 mL). The extract was washed with water (200 mL), dried over anhydrous magnesium sulfate, and the organic layer was evaporated under reduced pressure. The solid obtained was recrystallized from hexane (100 mL), and the filtered solid was dried under reduced pressure to obtain Compound (118) (9.0 g, 33.0 mmol).
To a flask including 2-bromotriphenylene, tetrahydrofuran (0.1 M) was added and then cooled to about -78 C. Then, 1.2 eq. of n-butyl lithium (n-BuLi, dissolved in hexane with a concentration of 1.6 M) was added and then stirred for about 30 minutes. 1.2 eq. of methylborate was added at the same temperature, and then, the temperature was gradually increased to ambient temperature. After stirring for about 1 hour, 50 ml of a 1N HCl solution was gradually added and then stirred for about 10 minutes. An organic layer was extracted with ethyl acetate (EA) and washed with distilled water. The product thus obtained was dried with magnesium sulfate (MgSO4) and distilled under a reduced pressure. The residue was recrystallized using ethyl acetate (EA):hexane (Hex) in a ratio of 1:10 to produce a triphenylen-2-ylboronic acid intermediate (Yield 77.4%). The mass of the compound identified using a high resolution mass spectrometer (HRMS) was 271. [HRMS for C18H13BO2 [M]+: calcd: 272.11, found: 271].

  • 3
  • [ 61676-62-8 ]
  • [ 19111-87-6 ]
  • [ 890042-13-4 ]
YieldReaction ConditionsOperation in experiment
83% 2- bromo triphenylene 10 g (32.55mmol) was dissolvedin the anhydrous tetrahydrofuran (100mL). The mixturethe n-butyl lithium 30 mL (48.83mmol) was gradually added to -78 after doing the cooling and it was stirred for 10 minutes. 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 26.57 mL (130.2mmol) was added in the reaction mixture and it reacted for 1 hour. After reaction was completed it dried to the MgSO 4 and 3times repetition extraction, and the extracted organic layer were recrystallized using the mixed solvent (waterchloroform: = 1 1: volume ratio) of chloroform and water after doing the concentration using the n-hexane and the compound 2-1 9.6 g (yield : 83%) was obtained.
83% 2-bromo-triphenylene 10g (32.55mmol) was dissolved in anhydrous THF (200mL). After the mixture was cooled to -78 C , n- butyl lithium was added 30mL (48.83mmol) slowly and stir for 10 minutes 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) to the reaction mixture, dioxaborolane-2) by the addition of 26.57mL (130.2mmol) was allowed to react for one hour. After the reaction was completed, a mixed solvent of water and chloroform (water: chloroform = 1: 1 volume ratio) and then using the extraction repeated three times, and drying the extracted organic layer with MgSO4 and concentrated, re-crystallized using n- hexane 9.6g to give the compound 2-1 (yield: 83%)
Preparation of Compound (115)In tetrahydrofuran (100 mL), 1-bromotriphenylene (Compound 114) (5.0 g, 16.2 mmol) was dissolved, and n-BuLi (2.5 M in n-hexane) (9.7 mL, 24.3 mmol) was slowly added dropwise thereto at -78 C. After stirring for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.0 g, 48.6 mmol) was added thereto at -78 C., and the resultant mixture was stirred at 25 C. for 2 hours. The reaction mixture was washed with water (100 mL), extracted with ethyl acetate (100 mL) and dried over anhydrous magnesium sulfate. Evaporation of the organic layer under reduced pressure and recrystallization from methanol (50 mL) gave solid, which was then filtered and dried to obtain Compound (115) (4.7 g, 10.0 mmol).
  • 4
  • [ 19111-87-6 ]
  • [ 654664-63-8 ]
YieldReaction ConditionsOperation in experiment
55% 2-bromotriphenylene (63.7, 207.4mmol) was dissolved in THF 1.5L and cooled to -78C. 10 minutes later, n-BuLi(2.5M in hexane) (125mL, 311mmol) was slowly added and the mixture was stirred for 1 hour. Triethylborate (67mL, 311mmol) was slowly added, and the mixture was stirred for 24 hours. After termination of the reaction, 1M HCl was added, and the mixture was extracted with EA. Subsequently, the residual moisture was removed using anhydrous MgSO4, after which drying and recrystallization from hexane were carried out, yielding Compound 7-1 (31.8g, 55%).
  • 5
  • [ 1257220-47-5 ]
  • [ 19111-87-6 ]
  • 12,12-dimethyl-10-triphenylen-2-yl-10,12-dihydro-10-azaindeno-[2,1-b]fluorene [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 40h;Inert atmosphere; Reflux; B1: 12,12-Dimethyl-10-triphenylen-2-yl-10,12-dihydro-10-azaindeno-[2,1-b]fluorene 48 g (0.17 mol) of <strong>[1257220-47-5]12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene</strong> (WO 2010/136109) and 45 g (0.16 mmol) of 2-bromotriphenylene (CAS 19111-87-6) are initially introduced in 2.5 l of xylene and degassed. After addition of 50 g (0.52 mol) of sodium tert-butoxide, the mixture is stirred for 15 minutes, and 10 ml (10 mmol) of tri-tert-butylphosphine and 1.5 g (6.7 mmol) of palladium acetate are subsequently added. The batch is heated under reflux for 40 h. When the reaction is complete, the reaction mixture is washed with water, the aqueous phase is extracted with toluene, and the combined organic phases are dried over sodium sulfate. The solvent is removed in a rotary evaporator, and the residue is extracted with hot toluene. Sublimation gives 69 g (0.14 mol, 80%) of the product having an HPLC purity>99.9%.
  • 6
  • [ 5419-55-6 ]
  • [ 19111-87-6 ]
  • [ 654664-63-8 ]
YieldReaction ConditionsOperation in experiment
100% 6.12 g of 2-bromo-triphenylene (molecular weight 306, 0.02 mol) Was dissolved in 100 ml of dry THF, -80 C was added n-butylamine 10 ml (2.5 M, 0.025 mol) Stirring for 15min, And 18 ml of triisopropyl borate was added dropwise. Hydrolysis, adjust the pH to neutral precipitation of white boronic acid derivatives 5.5g, the yield of nearly 100%.
 

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