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Structure of 1257220-47-5

Chemical Structure| 1257220-47-5

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Product Details of [ 1257220-47-5 ]

CAS No. :1257220-47-5
Formula : C21H17N
M.W : 283.37
SMILES Code : CC(C1=CC(NC2=C3C=CC=C2)=C3C=C14)(C)C5=C4C=CC=C5
MDL No. :MFCD26131198
InChI Key :UAVZDBIKIOWDQF-UHFFFAOYSA-N
Pubchem ID :66585204

Safety of [ 1257220-47-5 ]

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

Computational Chemistry of [ 1257220-47-5 ] Show Less

Physicochemical Properties

Num. heavy atoms 22
Num. arom. heavy atoms 19
Fraction Csp3 0.14
Num. rotatable bonds 0
Num. H-bond acceptors 0.0
Num. H-bond donors 1.0
Molar Refractivity 93.75
TPSA ?

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

15.79 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

2.9
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

5.89
Log Po/w (WLOGP)?

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

5.63
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.

4.81
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

6.1
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

5.07

Water Solubility

Log S (ESOL):?

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

-5.95
Solubility 0.00032 mg/ml ; 0.00000113 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.

-5.99
Solubility 0.000287 mg/ml ; 0.00000101 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

-8.51
Solubility 0.000000882 mg/ml ; 0.0000000031 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

High
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

Yes
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.

-3.85 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

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

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

0.0 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)

2.47

Application In Synthesis of [ 1257220-47-5 ]

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

  • Downstream synthetic route of [ 1257220-47-5 ]

[ 1257220-47-5 ] Synthesis Path-Downstream   1~35

  • 1
  • [ 108-36-1 ]
  • [ 1257220-47-5 ]
  • [ 1369587-63-2 ]
YieldReaction ConditionsOperation in experiment
30% With sodium t-butanolate;tri-tert-butyl phosphine; palladium diacetate; In toluene; at 120℃; for 24h; Compound 6-2 (15g, 53mmol), 1,3-dibromobenzene (32mL, 265mmol), Pd(OAc)2 (1.2g, 5mmol), P(t-Bu)3 (30mL, 64mmol), NaOt-Bu (25g, 265mmol) and toluene 300mL were mixed and stirred at 120C for 24 hours. After termination of the reaction, the mixture was cooled to room temperature and extracted with EA 1.5L, and the obtained organic layer was washed with distilled water 400mL. Subsequently, the solvent was removed under reduced pressure and the obtained solid was washed with hexane, filtered and dried. Silcia gel column chromatography and recrystallization were performed, yielding Compound 6-3 (7g, 30%).
With tris-(dibenzylideneacetone)dipalladium(0); potassium tert-butylate; In water; toluene; at 110℃; for 24h;Inert atmosphere; In a 500 mL three-necked flask, 0.03 mol was added under nitrogen protection.Raw material B-4,0.03molM-dibromobenzene,250 mL of toluene was stirred and mixed, and then 0.09 mol of potassium t-butoxide was added.0.0015 mol Pd2(dba)3, heated to 110 C, refluxing for 24 hours;Naturally cooled to room temperature, filtered, and the filtrate was subjected to vacuum distillation (-0.09 MPa, 85 C).Passing through a neutral silica gel column to obtain intermediate C-2;
  • 2
  • [ 1300115-10-9 ]
  • [ 1257220-47-5 ]
YieldReaction ConditionsOperation in experiment
85% With tetrafluoroboric acid; palladium diacetate; potassium carbonate; In ethylenediamine; at 200℃; for 12h;Inert atmosphere; Under an argon atmosphere, a compound C8 (46.7 g, 14.6 mmol), Pd(OAc)2 (1.64 g, 7.32 mmol), HBF4 (3.62 g, 14.6 mmol), and K2CO3 (60.5 g, 438 mmol) and dimethylamide (50 ml). The reaction mixture was stirred at 200 C for 12 hours. After the reaction was terminated, the mixture was extracted with ethyl acetate. Drying with anhydrous MgSO4The organic layer obtained is filtered and the organic phase is concentrated.Compound obtained by column chromatography C9 (35.17g, 85%.
76% With palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene; tricyclohexylphosphine; In N,N-dimethyl acetamide; at 170℃; for 8h; 2.1 Select 250ml three-necked flask, mechanical stirring rod, electric heating sleeve, weigh 12.7g HZ-1, 0.4g palladium acetate, 1.1g tricyclohexylphosphine, 11.8g DBU dissolved in 100ML DMAC, heating temperature to 170 C,Turn on the reaction;2.2 After 8 hours of reaction, the temperature was lowered to room temperature, and the reaction liquid was concentrated with an electric heating sleeve, and the product was dissolved in 200 ml.After washing with 200 ml of water for 5 times, the organic phase was dried to give a crude HZ-2.The crude product was pulverized with n-hexane to give 8.6 g, yield: 76%, HPLC: 99.9%.
73% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; caesium carbonate; In N,N-dimethyl acetamide; for 7h;Inert atmosphere; Reflux; Under nitrogen atmosphere, 25.0 g of N-(2-chlo- rophenyl)-9,9-dimethyl-fluorene-2-amine, 3.50 g of palladium(II) acetate, 7.70 g of di-tert-butyl(methyl)phosphoniumtetrafluoroborate, 127 g of cesium carbonate, and 600 mE of N,N-dimethylacetoamide were put into a flask and heated to reflux for seven hours while being stirred. Afier cooled down to the room temperature, the reaction solution was extracted with ethyl acetate. Afier an aqueous layer was removed, an organic layer was washed with a saturated saline solution. Afier dried with sodium sulfate, the organic layer was concentrated. The obtained residue was refined by silica-gel column chromatography and recrystallization, whereby 16.3 g (yield 73%) of a brown solid of an intermediate (F) was obtained.
53% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; In N,N-dimethyl acetamide; for 21h;Reflux; After mixing compound 1-1 (46 g, 143.8 mmol), Pd(OAc)2 (968 mg, 4.3 mmol), di-t-butyl(methyl)phosphoniumtetrafluoroborate (2 g, 4.31 mmol) and DMAc (200 mL), the reaction mixture was stirred for 21 hours under reflux. After terminating the reaction, the reaction mixture was filtered, and the filtered cake was washed with dichloromethane. The obtained organic layer was washed with purified water and dried with MgSO4, was concentrated under reduced pressure. And then, the crude oil was filtered through silica gel, and the remaining solution was concentrated under reduced pressure to obtain compound 1-2 (17 g, 53 %).
47% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; In N,N-dimethyl acetamide; at 200℃; for 12h; After mixing compound 1-1 (32 g, 0.1 mol), Pd(OAc)2 (1.1 g, 0.005 mol), di-t-butyl(methyl)phosphoniumtetrafluoroborate (2.48 g, 0.01 mol), K2CO3 (42 g, 0.30 mol) and DMA (550 mL), the reaction mixture was stirred for 12 hours at 200C. After terminating the reaction, the reaction mixture was extracted with EA. The obtained organic layer was dried with MgSO4, was filtered, was distillated under reduced pressure to remove the solvent, and was filtered through column to obtain compound 1-2 (14 g, 47 %).
47% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; at 200℃; for 12h; After mixing compound C-8-1 (32 g, 0.1 mol), Pd(OAc)2 (1.1 g, 0.005 mol), di-t-butylmethylphosphine·HBF4 (2.48 g, 0.01 mol), K2CO3 (42 g, 0.30 mol), and dimethyl amide (DMA) (550 mL), the mixture was stirred for 12 hours at 200C. After completing the reaction, the mixture was extracted with EA, and then the organic layer was dried with MgSO4. After filtering the obtained product, the solvent was removed under reduced pressure, and then the remaining product was separated with a column to obtain, white solid, compound C-8-2 (14 g, 47 %).
47% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; In N,N-dimethyl acetamide; at 200℃; for 12h; Compound 17-1 (32g, 0.1mol), Pd(OAc)2, (1.1g, 0.005mol), di-tert-butylmethylphosphine.HBF4 (2.48g, 0.01mol), K2CO3 (42g, 0.30mol), and DMA(550ml) were added, and then stirred at 200 for 12 hours. After completion of the reaction, extraction with ethyl acetate was performed on the resultant material, and then the organic layer is dried over MgSO4, followed by filtration. The solvent is removed under reduced pressure, followed by column chromatography, thereby obtaining Compound 17-2 (14g, 47 %).
43% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 5h;Reflux; In a flask was added Intermediate 18-3 (40g, 0,125mol), sodium carbonate (40g, 0.38mol), palladium acetate (0.5g, 2.2mmol), tricyclohexylphosphine tetrafluoroborate (1.6g, 4.4 mmol) and dimethylacetamide (0.5L), was heated at reflux for 5 hours, cooled, the solvent was evaporated under reduced partially removed, cooled, added to water, extracted with ethyl acetate, dried, purified by column to give the product 15g, yield 43%.
43% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 5h;Reflux; In a flask, intermediate 2-1 (40 g, 0.125 mol), sodium carbonate (40 g, 0.38 mol), palladium acetate (0.5 g,2.2 mmol), tricyclohexylphosphine tetrafluoroborate (1.6 g, 4.4 mmol) and dimethylacetamide (0.5 L) were heated at reflux for 5 hours, cooled, steamed to remove some of the solvent, cooled, and added to water. Ethyl acetate extraction, drying, and column purification gave 15 g of product in 43% yield.
43% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 5h;Reflux; In the flask,Intermediate 1-1 (40 g, 0.125 mol) was added,Sodium carbonate (40g, 0.38mol),Palladium acetate (0.5g, 2.2mmol),Tricyclohexylphosphine tetrafluoroborate (1.6 g, 4.4 mmol)And dimethylacetamide (0.5L),Heat reflux for 5 hours, cool,Steam distillation to remove some of the solvent,Cool, add water,Extract with ethyl acetate, dry,After column purification gives 15g product,Yield 43%.
42% With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; In N,N-dimethyl acetamide; for 24h;Reflux; To a solution of compound 9-1 (2.5 g, 7.8 mmol), di-tert-butylmethylphosphonium tetrafluoroborate ((t-Bu) 2PMeHBF4, 0.057 g, 0.23 mmol), Pd (OAc) 2 (0.05 g, 0.23 mmol) was dissolved in dimethylacetamide (DMAC, 80 ml) and refluxed with stirring for 24 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure and extracted with methylene chloride and water. The extract was subjected to column chromatography using toluene: Hx to obtain Compound 9-2 (0.9 g, 42%).
36% With sodium carbonate;palladium diacetate; tricyclohexylphosphine tetrafluoroborate; In ISOPROPYLAMIDE; at 190℃; for 3h; Compound 6-1 (70g, 218mmol), Pd(OAc)2 (2.4g, 11mmol), PCy3HBF4 (8g, 22mmol), Na2CO3 (70g, 654mmol) and DMA 1.2L were mixed and stirred at 190C for 3 hours. After termination of the reaction, the mixture was extracted with EA 1L, and the obtained organic layer was washed with distilled water 200mL and dried with anhydrous MgSO4, and the organic solvent was removed under reduced pressure. The obtained solid was separated using silica gel column chromatography and recrystallization, yielding Compound 6-2 (22g, 36%).
36% With sodium carbonate; tricyclohexylphosphine tetrafluoroborate;palladium diacetate; In ISOPROPYLAMIDE; at 190℃; for 3h; Compound 12-1 (70g, 218mmol), Pd(OAc)2 (2.4g, 11mmol,) tricyclohexylphosphine tetrafluoroborate (8g, 22mmol), Na2CO3 (70g, 654mmol) and DMA (1.2L) were mixed, and stirred at 190C for 3 hours. After stirring, the reaction mixture was cooled to room temperature and extracted with EA. Column separation was conducted on the solid product, yielding Compound 12-2 (22g, 36%).
36% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; at 190℃; for 3h; After mixing compound 10-1 70 g (218 mmol), Pd(OAc)2 2.4 g (11 mmol), PCy3HBF4 8 g (22 mmol), Na2CO3 70 g (654 mmol), and dimethylacetamide (DMA) 1.2 L, the mixture was stirred at 190 C for 3 hours. After completing the reaction, the mixture was extracted with ethylacetate 1 L, the obtained organic layer was washed with distilled water 200 mL, and dried with anhydrous MgSO4. Then, the organic solvent was removed under reduced pressure. Then, the obtained solid was separated using silica gel column chromatography and recrystallization to obtain compound 10-2 22 g (36%).
36% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; at 190℃; for 3h; Compound 8-1 (70.0 g, 218.0 mmol), Pd(OAc)2 (2.4 g, 11.0 mmol), tricyclohexylphosphine tetrafluoroborate (PCy3HBF4) (8.0 g, 22.0 mmol), Na2CO3 (70.0 g, 654.0 mmol), and dimethylacetamide (DMA) (1.2 L) were mixed in a flask and stirred at 190C for 3 hrs. After completing the reaction, the mixture was extracted with EA (1.0 L), and the obtained organic layer was washed with distilled water (200.0 mL) and dried over anhydrous MgSO4. The organic solvent was removed under reduced pressure. After the separation of the obtained solid via column chromatography on silica gel and recrystallization, compound 8-2 (22.0 g, 36 %) was obtained.
36% With palladium diacetate; sodium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; at 190℃; for 3h; 70 g (218 mmol) of compound 10-1, 2.4 g (11 mmol) of Pd (OAc) 2, 8 g (22 mmol) PCy3HBF4, 70 g (654 mmol) of Na 2 CO 3 and 1.2 L of dimethylacetamide (DMA) were mixed and stirred at 190 C. for 3 hours. After the reaction, the mixture was extracted with 1 L of ethyl acetate, the organic layer was washed with 200 mL of distilled water, dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give 22 g (36%) of compound 10-2.

  • 3
  • [ 1262866-93-2 ]
  • [ 1257220-47-5 ]
  • [ 1373227-56-5 ]
YieldReaction ConditionsOperation in experiment
70% Compound 12-2 (5g, 17.64mmol) and DMF (100mL) were mixed, and NaH (1.1g, 26.46mmol, 60% dispersion in mineral oil) was slowly added to the mixture. The mixture was stirred at room temperature for 30 minutes. After stirring, 4-(biphenyl-4-yl)-2-chloroquinazoline(5.6g, 17.64mmol) was slowly added to the mixture and stirred for 4 hours. After stirring, a solid product was obtained by adding distilled water (300mL) to the reaction mixture and stirring the reaction mixture for 30 minutes. Column separation was conducted on the solid product, yielding Compound 3 (6.9g, 70%). MS/EIMS: 563.69(found), 563.24(calculated)
  • 4
  • [ 1257220-47-5 ]
  • [ 1413615-86-7 ]
  • [ 1419576-90-1 ]
YieldReaction ConditionsOperation in experiment
36% After dissolving compound 1-2 (6.6 g, 18.6 mmol) in DMF (120 mL), NaH (813 mg, 20.3 mmol) was added at 0C, and was stirred for 10 minutes. Compound 1-3 (4.8 g, 16.9 mmol) was added to the reaction mixture, and was stirred for 19 hours. After terminating the reaction, MeOH was added to the reaction mixture. The obtained solid was filtered through silica gel, was recrystallized with DMF to obtain compound C-40 (4 g, 36 %).[99]MS/FAB found 603; calculated 602.73
  • 5
  • [ 1257220-47-5 ]
  • [ 1383627-88-0 ]
  • [ 1420118-21-3 ]
YieldReaction ConditionsOperation in experiment
50% After dissolving compound 1-2 (3.27 g, 11.5 mmol) in DMF (80 mL), NaH (507 mg, 12.7 mmol) was added at 0C, and was stirred for 10 minutes. Compound 2-1 (4.2 g, 12.1 mmol) was added to the reaction mixture, and was stirred for 7 hours. After terminating the reaction, MeOH was added to the reaction mixture. The obtained solid was filtered through silica gel, was recrystallized with DMF to obtain compound C-56 (3.4 g, 50 %).[115]MS/FAB found 590; calculated 589.73
  • 6
  • [ 1257220-47-5 ]
  • [ 1420067-46-4 ]
  • [ 1420120-27-9 ]
YieldReaction ConditionsOperation in experiment
48% After dissolving 60% NaH (1.0 g, 0.025 mol) in DMF (40 mL), the solution was stirred. After dissolving compound 1-2 (5.0 g, 0.017 mol) in DMF (40 mL), the solution was added to the above NaH solution, and was stirred for 1 hour. After dissolving compound 11-3 (7.2 g, 0.017 mol) in DMF (20 mL), and stirring, the mixed solution of compound 1-2 was added to the mixed solution of compound 11-3, and was stirred for 12 hours. The obtained yellow solid was filtered, was washed with MeOH, and was recrystallized to obtain compound C-41 (5 g, 48 %)[205]MS/FAB found 590; calculated 589.73
  • 7
  • [ 1257220-47-5 ]
  • [ 1383628-03-2 ]
  • [ 1420118-08-6 ]
YieldReaction ConditionsOperation in experiment
18% With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 20℃; for 12h; After dissolving compound 1-2 (4.5 g, 15.89 mmol) and compound 1-5 (7.3 g, 19.07 mmol) in dimethylformamide (DMF) (130 mL), 60% NaH in mineral oil (0.76 g, 19.07 mmol) was slowly added to the mixture, and was stirred for 12 hours at room temperature. After terminating the reaction, MeOH was added to the reaction mixture. The obtained solid was filtered through silica gel, was recrystallized with EA and DMF to obtain compound C-55 (1.8 g, 18 %). [108] MS/FAB found 630; calculated 629.79
  • 8
  • [ 1257220-47-5 ]
  • [ 914450-89-8 ]
  • [ 1346011-00-4 ]
YieldReaction ConditionsOperation in experiment
53% With potassium phosphate; tri-tert-butyl phosphine; palladium diacetate; In para-xylene; for 42h;Inert atmosphere; Reflux; [0155] 21.0 g (23.6 mmol) of compound IX, 53.4 g (188.4 mmol) of compound II and 203 g (960 mmol) of K3 PO4 are suspended in 3000 ml of p-xylene. 164 mg (0.73 mmol) of Pd(OAc)2 and 9.4 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 42 h. After cooling, the organic phase is separated off, washed three times with 400 ml of water and subsequently evaporated to dryness. The residue is washed with ethanol and recrystallised from toluene and finally dried under reduced pressure. The yield is 20.6 g (12.3 mmol), corresponding to 53% of theory.
  • 9
  • [ 1357150-72-1 ]
  • [ 1257220-47-5 ]
YieldReaction ConditionsOperation in experiment
85% With palladium diacetate; potassium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 12h;Reflux; 70 g (0.19 mol) of synthesized in Scheme 23, 1.4 g (0.004 mol) of tricyclohexylphosphinium tetrafluoroborate, 0.431 g (0.002 mol) of palladium acetate,53.1 g (0.384 mol) of potassium carbonate and 700 ml of N, N-dimethylacetamide were added and refluxed for 12 hours. After the completion of the reaction, the mixture was extracted and the organic layer was concentrated under reduced pressure and recrystallized with hexane to obtain 46.3 g (yield 85%).
85% With palladium diacetate; potassium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 12h;Reflux; In a 2 L round bottom flask, 70 g (0.19 mol) of the compound represented by formula 4-c obtained from Scheme 9, 1.4 g (0.004 mol) of tricyclohexylphosphinium tetrafluoroborate, 0.431 g (0.002 mol) of palladium acetate,Potassium carbonate 53.1 g (0.384 mol) and 700 mL of N,N-dimethylacetamide were added and refluxed for 12 hours. After completion of the reaction, extraction, the organic layer was concentrated under reduced pressure, recrystallized with hexane, and dried to obtain 46.3g (85%).
85% With palladium diacetate; potassium carbonate; tricyclohexylphosphine tetrafluoroborate; In N,N-dimethyl acetamide; for 12h;Reflux; In a 2L round bottom flask, 70 g (0.19 mol) of the compound of formula 5-b obtained from Scheme 9, 1.4 g (0.004 mol) of tricyclohexylphosphinium tetrafluoroborate, 0.431 g (0.002 mol) of palladium acetate, and potassium carbonate 53.1 g (0.384 mol) and 700 mL of N,N-dimethylacetamide were added and refluxed for 12 hours. After the reaction was completed, the organic layer was concentrated under reduced pressure, recrystallized from hexane and dried to obtain 46.3 g (85%) of .10-c
55.2% With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl-formamide; at 100℃; for 11h;Inert atmosphere; Example 1 Synthesis of 12,12-dimethyl-10-phenyl-7-(9-phenyl-9H-carbazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole (Compound 5) N-(9,9-dimethyl-9H-fluorene-2-yl)-2-bromo-aniline (18.5 g), potassium acetate (6.98 g), and DMF (95 ml) were added to a nitrogen-substituted reaction vessel and aerated with nitrogen gas for 1 hour. The mixture was heated after adding tetrakis(triphenylphosphine)palladium (1.18 g) and stirred at 100C for 11 hours. After the mixture was cooled to a room temperature, the reaction liquid was added to water (300 ml) and extraction was performed with toluene (300 ml). An organic layer obtained was washed with water (200 ml) twice, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel; eluent: toluene/n-hexane) to obtain a pale yellow powder of 12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole (7.9 g; yield 55.2%).
55.2% With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl-formamide; at 100℃; for 12h;Inert atmosphere; In the reaction vessel replaced by nitrogen, add:N-(9,9-dimethyl-9H-fluorene-2-yl)-2-bromoaniline18.5g,Potassium acetate 6.98g, DMF: 95ml, nitrogen aeration for 1 hour.Add four (triphenylphosphine) palladium1.18g and heated, and stirred at 100C for 11 hours. The reaction solution was cooled to room temperature, and 300ml of water was poured into it,300 ml of toluene was used for extraction.The organic layer was washed twice with 200 ml of water, dehydrated with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a crude product.Chromatography Analyzer for Crude Material Utilization Column(Carrier: silica gel, eluent: toluene/n-hexane) refined to obtain12,12-Dimethyl-10,12-indan[2,1-b]carbazoleYellow powder7.9g (yield 55.2%).

  • 10
  • [ 92-66-0 ]
  • [ 1257220-47-5 ]
  • [ 1257248-17-1 ]
YieldReaction ConditionsOperation in experiment
88.1% With 3,5-ditertbutyl salicylic acid; copper; potassium carbonate; sodium hydrogensulfite; at 190℃; for 26h;Inert atmosphere; Example 6 Synthesis of 10-(biphenyl-4-yl)-12,12-dimethyl-7-(9-phenyl-9H-carbazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole (Compound 122) <strong>[1257220-47-5]12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole</strong> synthesized in Example 1 (35.5 g), 4-bromobiphenyl (35.0 g), sodium bisulfite (6.0 g), a copper powder (2.4 g), 3,5-di(tert-butyl)salicylic acid (9.4 g), potassium carbonate (31.2 g), and dodecylbenzene (52 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 190C for 26 hours. After cooled to 120C, the mixture was stirred after adding toluene (35 ml), and a crude product was collected by filtration. After adding toluene (1.6 L) to the crude product, the crude product was heated and extracted at 110C. After cooled to a room temperature, the crude product was concentrated under reduced pressure. The product was crystallized with methanol (120 ml) to obtain a white powder of 10-(biphenyl-4-yl)-<strong>[1257220-47-5]12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole</strong> (48.5 g; yield 88.1%). The resulting 10-(biphenyl-4-yl)-<strong>[1257220-47-5]12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole</strong> (42.5 g) and DMF (2.5 L) were added to a reaction vessel, and the mixture was heated up to 70C and dissolved.
88.1% With 3,5-ditertbutyl salicylic acid; copper; potassium carbonate; sodium hydrogensulfite; at 190℃; for 26h;Inert atmosphere; In the reaction vessel replaced by nitrogen, add:35.5 g of 12,12-dimethyl-10,12-indan[2,1-b]carbazole synthesized in Example 1,4-bromobiphenyl 35.0g,6.0g of sodium bisulfite, 2.4g of copper powder, 9.4g of 3,5-bis(tert-butyl)salicylic acid,31.2 g of potassium carbonate and 52 ml of dodecylbenzene were heated and stirred at 190C for 26 hours. It was cooled to 120C, 35 ml of toluene was added and stirred, and the crude product was collected by filtration.1.6L of toluene was added to the crude product and heated, and after extraction was performed at 110C,Cool to room temperature and concentrate under reduced pressure. Use 120ml methanol for crystallization,Obtain 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-indane [2,1-b]Carbazole48.5g of white powder (yield 88.1%).
  • 11
  • [ 1257220-47-5 ]
  • [ 28320-31-2 ]
  • [ 1357150-87-8 ]
YieldReaction ConditionsOperation in experiment
80.0% With 3,5-ditertbutyl salicylic acid; copper; potassium carbonate; sodium hydrogensulfite; at 180℃; for 29h;Inert atmosphere; Example 8 Synthesis of 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-7-(9-phenyl-9H-carbazol-3-yl)-10,12-dihydroindeno[2,1-b]carbazole (Compound 124) 12,12-Dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (5.5 g), 2-bromo-9,9-dimethyl-9H-fluorene (6.4 g), sodium bisulfite (0.3 g), a copper powder (0.1 g), 3,5-di(tert-butyl)salicylic acid (0.5 g), potassium carbonate (4.0 g), and dodecylbenzene (5 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 180C for 29 hours. The mixture was cooled to 100C, and insoluble matter was removed by filtration after adding toluene (80 ml), and a filtrate was concentrated. Crystallization using n-hexane (20 ml) was performed to obtain an ocher powder of 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-10,12-dihydroindeno[2,1-b]carbazole (7.4 g; yield 80.0%) The resulting 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-10,12-dihydroindeno[2,1-b]carbazole (7.0 g) and DMF (140 ml) were added to a reaction vessel.
  • 12
  • [ 591-50-4 ]
  • [ 1257220-47-5 ]
  • [ 1257220-43-1 ]
YieldReaction ConditionsOperation in experiment
97% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Reflux; 100 g (353 mmol) of indenocarbazole, A suspension of 5 mL (529 mmol) of iodobenzene, 16 g (17 mmol) of Pd2(dba)3, 17 mL (35 mmol) of tri-tert-butylphosphine and 102 g (1,059 mmol) of sodium tertiary butoxide was suspended in 1,500 mL of toluene Followed by reflux stirring for 12 hours. The mixture was extracted with dichloromethane and distilled water, and the organic layer was subjected to silica gel filtration. The organic solution was removed and silica gel column was obtained to obtain 124 g (yield: 97%) of 1,1-dimethyl-3-phenyl-1,3-dihydroindeno [2,1- b] carbazole.
88.3% With 3,5-ditertbutyl salicylic acid; copper; potassium carbonate; sodium hydrogensulfite; at 170℃; for 10h;Inert atmosphere; The resulting <strong>[1257220-47-5]12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole</strong> (7.8 g), iodobenzene (3.7 ml), sodium bisulfite (0.43 g), a copper powder (0.17 g), 3,5-di(tert-butyl)salicylic acid (0.69 g), potassium carbonate (5.71 g), and dodecylbenzene (10 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 170C for 10 hours. The mixture was cooled to 100C, extracted by adding toluene (100 ml), concentrated under reduced pressure, and crystallized using n-hexane (30 ml) to obtain a pale yellow powder of 12,12-dimethyl-10-phenyl-10,12-dihydroindeno[2,1-b]carbazole (8.73 g; yield 88.3%).
88.3% With 3,5-ditertbutyl salicylic acid; copper; potassium carbonate; sodium hydrogensulfite; at 170℃; for 10h;Inert atmosphere; The obtained 12,12-dimethyl-10,12-indan[2,1-b]carbazole 7.8g,With 3.7ml of benzene iodide, 0.43g of sodium bisulfite, 0.17g of copper powder,3,5-bis(tert-butyl)salicylic acid 0.69g, potassium carbonate 5.71g,Dodecylbenzene 10ml,Add to the nitrogen-replaced reaction vessel and heat,Stir at 170C for 10 hours. Cool to 100C,After adding 100ml of toluene for extraction, it was concentrated under reduced pressure.Furthermore, 30ml of n-hexane was used for crystallization to obtainThe lightness of 12,12-dimethyl-10-phenyl-10,12-indan[2,1-b]carbazole8.73g yellow powder (yield 88.3%).
  • 13
  • [ 589-87-7 ]
  • [ 1257220-47-5 ]
  • [ 1361126-22-8 ]
YieldReaction ConditionsOperation in experiment
88% With potassium phosphate; copper(l) iodide; ethylenediamine; In toluene; at 120℃; for 18h; After mixing 1,3-dihydro-3,3-dimethylindeno[2,1-b]carbazole (5 g, 17.6 mmol), 4-bromoiodobenzene (12.5 g, 44 mmol), CuI (1.7 g, 8.8 mmol), K3PO4 (11 g, 53 mmol), EDA (2.4 mL, 35 mmol), and toluene 90 mL, the mixture was stirred for 18 hours at 120C. After completing the reaction, the mixture was washed with distilled water, and then extracted with EA. The organic layer was dried with MgSO4, and solvent was removed with a rotary evaporator. Then, the crude product was filtered through silica using methylene chloride (MC) to obtain, white solid, compound 2-1 (6.8 g, 88 %).
80% With copper(l) iodide; potassium carbonate; rac-diaminocyclohexane; In dimethyl sulfoxide; at 110℃; for 16h;Inert atmosphere; 5,7-Dihydro-7,7-dimethyl-indolo[2,1-b]carbazole (33.9 g, 119.6 mmol), 1-bromo-4-iodobenzene (38.0 g, 134.3 m) Molar), cuprous iodide (I) (4.55 g, 23.9 mmol), dimethyl sulfoxide (250 ml), potassium carbonate (33.1 g, 239.2 mmol) and 1,2-diaminocyclohexane (6.8 g, 59.8 mmol) were sequentially added to a 500 ml double neck round bottom reaction flask, and the reaction system was filled with nitrogen. The system was heated to 110 C in an oil bath. After 16 hours, the system was cooled and the reaction was poured. After stirring in 300 ml of water, and then extracting with ethyl acetate, the extract was washed with saturated brine, then water was removed with magnesium sulfate and filtered, and the filtrate was removed by a rotary evaporator, and silica gel column chromatography was used. Ethyl acetate and hexane were used as eluents to give a light brown solid which was compound 2-5-b (41.9 g, 80%).
74.3% With tris-(dibenzylideneacetone)dipalladium(0); 18-crown-6 ether; tri-tert-butyl phosphine; potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; for 12h;Reflux; 43 g (0.151 mol) of synthesized in Scheme 24, 51.3 g (0.181 mol) of 1-bromo-4-iodobenzene, tris (dibenzideneacetone) dipalladium 0) 1.3 g (0.001 mol), 1.2 g (0.42 mmol) of 18-crown-6-ether,0.9 g (0.004 mol) of tritary butylphosphine,41.7 g (0.302 mol) of potassium carbonate and 800 ml of xylene were added and refluxed for 12 hours. After the completion of the reaction and extraction, the organic layer was concentrated under reduced pressure and recrystallized with hexane to give 49.2g (yield 74.3%) of .
57% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Inert atmosphere; Reflux; To the reaction flask was added Intermediate 18-4 (10g, 35.3mmol), p-bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium acetate (0.3g, 1.3mmol), tri-tert-butylphosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150 mL), under nitrogen was heated at reflux for 24 hours, cooled, toluene was removed, dichloromethane was added, washed with water, dried, the crude product by column to give product 10g, yield 57%.
57% With tri-tert-butylphosphine tetrafluoroborate; potassium tert-butylate; palladium diacetate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask was added 7,7-dimethyl-5H-indeno [2,1-b] carbazole (10 g, 35.3 mmol)P-bromobenzene (12 g, 42 mmol),Potassium tert-butoxide (7.9 g, 70.6 mmol)Palladium acetate (0.3 g, 1.3 mmol)Tri-tert-butylphosphonium tetrafluoroborate (0.8 g, 2.7 mmol)And toluene (150 mL),Nitrogen protectionUnder reflux for 24 hours,Cooling, removing toluene, adding methylene chloride, washing with water,Dried, and the crude product was passed through a column to give 10 g of product in 57% yield.
57% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask was added 7,7-dimethyl-5H-indeno [2,1-b] carbazole (10 g, 35.3 mmol)P-bromobenzene (12 g, 42 mmol),Potassium tert-butoxide (7.9 g, 70.6 mmol)Palladium acetate (0.3 g, 1.3 mmol)Tri-tert-butylphosphonium tetrafluoroborate (0.8 g, 2.7 mmol) andToluene (150 mL),Under nitrogen was heated under reflux for 24 hours.After cooling, remove the toluene, add dichloroMethane, washed, dried, coarse product column,10 g of product was obtained in a yield of 57%.
57% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask were added Intermediate 2-2 (10 g, 35.3 mmol), p-bromoiodobenzene (12 g, 42 mmol), potassium tert-butoxide(7.9 g, 70.6 mmol), palladium acetate (0.3 g, 1.3 mmol), tri-tert-butylphosphine tetrafluoroborate (0.8 g, 2.7 mmol) and toluene(150 mL), heated to reflux under nitrogen for 24 hours, cooled, removed toluene, added dichloromethane, washed with water, dried, crude productThe column was passed to give 10 g of product in 57% yield.
57% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Inert atmosphere; Reflux; Add to the reaction flaskIntermediate 1-2 (10 g, 35.3 mmol),Bromo iodobenzene (12 g, 42 mmol),Potassium tert-butoxide (7.9 g, 70.6 mmol),Palladium acetate (0.3g, 1.3mmol),Tri-tert-butylphosphine tetrafluoroborate (0.8g, 2.7mmol)And toluene (150mL),Heated under nitrogen for 24 hours under refluxCool, remove toluene,Add dichloromethane, wash,Dry, crude product column,10 g of product was obtained with a yield of 57%.
With potassium phosphate; copper(l) iodide; ethylenediamine; In toluene; at 140℃; for 12h; Compound 17-2 (32g, 0.11mol), 1-bromo-4-iodobenzene (95.8g, 0.339mol), CuI (13g, 0.068mol), K3PO4(86.3g,0.41mol), and toluene(700ml) were put into a 500mL round-bottom flask, and the resultant mixture was stirred at 80 for 10 minutes. Then, ethylenediamine (18.3ml, 0.27mol) was added thereinto, followed by stirring at 140 for 12 hours. After completion of the reaction, extraction with ethyl acetate was performed on the resultant material, followed by column chromatography, thereby obtaining a compound. This compound (46g, 0.01mol) was put into a 2000mL round-bottom flask of anhydrous condition, followed by addition of dried THF (800ml) thereinto, and then n-BuLi (63ml, 2.25M solution in hexane) was added thereinto at -78 while stirring under nitrogen. The resultant mixture was stirred at -78 for 1 hour, followed by slow addition of B(O-iPr);(48m1, 0.21mol) thereinto at -78 , and then the temperature was raised to room temperature, followed by reaction for 12 hours. After completion of the reaction, extraction with ethyl acetate was performed on the resultant material, and then the organic layer is dried over MgSO4, followed by filtration. The solvent is removed under reduced pressure, followed by recrystallization, thereby obtaining Compound 18-1 (32.8g, 78%) as white solids.

  • 14
  • [ 1257220-47-5 ]
  • [ 1257247-97-4 ]
YieldReaction ConditionsOperation in experiment
97% With N-Bromosuccinimide; In acetonitrile; for 1h;Inert atmosphere; Cooling with ice; Under an argon atmosphere, into a mixture of 5.60 g (19.8 mmol) of the intermediate 19 in 99 mL of acetonitrile, 3.52 g (19.8 mmol) of N-bromosuccinimide was added under ice-cooling. The resultant mixture was stirred for one hour. (0262) After the reaction, the mixture was heated to room temperature and the generated solid was collected by filtration. The filtrate was extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, filtered, and then concentrated. The concentrate residue and the solid collected by filtration was combined and purified by silica gel column chromatography to obtain 6.93 g (yield: 97%) of solid, which was identified as the following intermediate 20 by FD-MS analysis.
78% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 6.17h; After mixing 1,3-dihydro-3,3-dimethylindeno[2,1-b]carbazole (10 g, 0.035 mol) and dimethylformamide (DMF) 500 mL, the mixture was stirred for 10 minutes at 0C. Then, dissolving n-bromosuccinimide (NBS) (6.0 g, 0.03 mol) in DMF 350 mL, the solution was added to the above mixture, and the mixture was stirred for 6 hours at 0C. After completing the reaction, the mixture was neutralized with distilled water, and then extracted with ethyl acetate (EA). The organic layer was dried with MgSO4, and solvent was removed with a rotary evaporator. Then, the remaining product was purified by column chromatography using EA as a developing solvent to obtain compound 1-1 (10 g, 78 %).
78% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 6h;Inert atmosphere; The chemical reaction equation is as follows:Nitrogen atmosphere, 0 C,N-bromosuccinimide (NBS) (1.25 g, 7 mmol)A solution of 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole (1.98 g, 7 mmol) in 100 mL of DMF was added in three batches; the reaction was carried out at 0 CAfter 6 hours,Add deionized water to quench, the end of the reaction; extracted with methylene chloride, organic phase combined with anhydrous magnesium sulfate dry, spinThe crude product was passed through a column of petroleum ether / dichloromethane and the product was collected and dried to give 1.98 g of a white powder in 78% yield.
68.9% With bromine; acetic acid; at 0 - 20℃; for 12h; 3) In a three-neck 250 ml bottle, add 0.04 mol of intermediate 2-2, 100 ml of acetic acid, stir to dissolve, and bathe with ice salt.At 0C, 0.05 mol of Br2 was dissolved in 50 ml of acetic acid. The bromine acetic acid solution was slowly added dropwise to the above reaction system. After the addition, the temperature was raised to room temperature and the reaction was stirred for 12 hours. Body 2-2 remains, reaction is complete; add NaOHThe aqueous solution is neutralized and the solution is extracted with dichloromethane. The layers are separated, the organic phase is filtered, and the filtrate is evaporated to a zero fraction.After neutral silica gel column, intermediate 2-3 was obtained, HPLC purity 99.3%, yield 68.9%;
65% With N-Bromosuccinimide; In tetrahydrofuran; at 0℃; for 16.5h; Example 5a Synthesis of 7-bromo-<strong>[1257220-47-5]12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene</strong> 56.7 g (200 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene [1257220-47-5] are initially introduced in 1500 ml of THF. The reaction mixture is cooled to 0 C., and 35.6 g (200 mmol) of N-bromosuccinimide are added in portions over the course of 30 minutes. The cooling is removed, and the mixture is stirred for 16 hours and subsequently evaporated to about 250 ml. 1000 ml of water are added with vigorous stirring, and the solid formed is filtered off with suction and washed by boiling twice with 800 ml of ethanol each time. Drying in vacuo leaves 47.1 g (130 mmol, 65% of theory) of the product as a colourless solid having a purity of about 98% according to 1H-NMR.
56% With N-Bromosuccinimide; In acetonitrile; at -15 - 20℃; for 4h; Step 1: 7-Bromo-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene 66.5 g (234.6 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene are initially introduced in 1000 ml of acetonitrile. A solution of 41.7 g (234.6 mmol) of NBS in 500 ml of CH3CN is subsequently added dropwise at -15 C. with exclusion of light, the mixture is allowed to come to room temperature and is stirred at this temperature for a further 4 h. 150 ml of water are subsequently added to the mixture, which is then extracted with CH2Cl2. The organic phase is dried over MgSO4, and the solvents are removed in vacuo. The product is washed by stirring with hot hexane and filtered off with suction. Yield: 47.5 g (131 mmol), 56% of theory, purity according to 1H-NMR about 97%.
With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0 - 20℃; for 6h; Weigh compound 9 (1 g, 3.53 mmol) into a 100 mL round bottom flask, add 20 mL of DMF and stir to dissolve, add NBS (817 mg, 4.59 mmol) in batches under ice bath conditions, the reaction system slowly from the ice bath Return to room temperature and react for 6 hours. After the reaction is completed, add water to quench, extract 7 times with dichloromethane and water to remove DMF, dry over anhydrous sodium sulfate, and remove the solvent by evaporation under reduced pressure. reaction.
With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0 - 20℃; for 6h; Weigh compound 9 (1 g, 3.53 mmol) in a 100 mL round bottom flask,Add 20 mL of DMF and stir to dissolve. Add NBS (817 mg, 4.59 mmol) in batches on ice bath. The reaction system was slowly returned to room temperature from the ice bath and reacted for 6 hours. After the reaction was completed, water was added to quench.Extract 7 times with dichloromethane and water to remove DMF, dry with anhydrous sodium sulfate,The solvent was evaporated under reduced pressure, and after spin-drying, the product 10 was directly used in the next reaction without purification.
With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; for 8.5h;Darkness; Into a 1L reaction flask, add compound A-1 (7.08g, 25.0mmol) and N,N-dimethylformamide (600ml) in sequence, stir to dissolve compound A-1, subsequently, N-bromosuccinimide (NBS) (4.45g, 25.0mmol) was slowly added to the reaction flask within 30 minutes at room temperature and protected from light, the mixture was stirred for 8 hours and then poured into sodium carbonate solution (3M, 1.2L).

  • 15
  • [ 28320-31-2 ]
  • [ 95-51-2 ]
  • [ 1257220-47-5 ]
YieldReaction ConditionsOperation in experiment
77.6% With tris-(dibenzylideneacetone)dipalladium(0); potassium tert-butylate; tri tert-butylphosphoniumtetrafluoroborate; In 5,5-dimethyl-1,3-cyclohexadiene; for 18h;Inert atmosphere; Reflux; 9.9-Dimethyl-2-bromoindole was sequentially introduced into a dry 5L four-necked flask.273.2 g (1.0 mol, 99%, 1.0 eq.),O-chloroaniline153.1 g (1.2 mol, 99%, 1.2 eq.),Pd2dba3 catalyst4.58g (0.005mol, 97%, 0.5% eq.),t-Bu3PHBF4 ligand 2.9 g (0.01 mol, 99%, 1% eq.),Potassium tert-butoxide 224.4g (2mol, 98%, 2.0eq.) and xylene 2.8kg,Nitrogen was replaced three times and heated under reflux for 18 h under nitrogen.The reaction of the reaction, 9,9-dimethyl-2-bromoindole, was completely converted by TLC.After the reaction was completed, the temperature was lowered to room temperature, and quenched by adding 500 g of ice water, stirred for 1 hour, and layered.The organic phase is retained; the organic phase is washed twice with 2*250g water;The organic phase is concentrated to recover the solvent xylene; a brown red viscous liquid is obtained.Recrystallization from dichloromethane and n-hexane afforded 219.9 g of pale yellow solid.The yield was 77.6%.
  • 16
  • [ 1257220-47-5 ]
  • [ 23674-20-6 ]
  • [ 1604713-94-1 ]
YieldReaction ConditionsOperation in experiment
46.5% With potassium phosphate; copper(l) iodide; ethylenediamine; In toluene; at 120℃; for 12h; After mixing compound A 4.5 g (0.016 mol), 9-bromo-10-phenylanthracene 6.3 g (0.019 mol), CuI 1.5 g (0.008 mol), K3PO4 10.4 g (0.049 mol), ethylenediamine (EDA) 1.1 mL (0.016 mol), and toluene 150 mL, the mixture was heated to 120C, and stirred for 12 hours. After the reaction was completed, the mixture was washed with distilled water, extracted with ethylacetate (EA), the organic layer was dried with MgSO4, the solvent was removed using a rotary evaporator, and the remaining product was separated using a column to obtain compound H-1, 4.0 g (46.5%). Melting point 307C, UV 268 nm (in methylene chloride (MC)), PL 420 nm (in MC), Molecular weight 535.68
  • 17
  • [ 3842-55-5 ]
  • [ 1257220-47-5 ]
  • C36H26N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
42.96% With sodium hydride; In N,N-dimethyl-formamide; at 20℃; for 12h; Compound 17-2 (5g, 17.64mmol) and 2-Chloro-4,6-diphenyltriazine (5.6g, 21.17mmol) were dissolved in DMF (100ml). NaH (1.05g, 26.46mmol) was slowly added thereinto, followed by stirring at room temperature for 12 hours. Distilled water was added thereinto, and the solids were filtered under reduced pressure, followed by column chromatography, thereby obtaining Compound 95 (3.9g, 42.96%). MS/FAB found 514, calculated 514.62
  • 18
  • [ 474688-76-1 ]
  • [ 1257220-47-5 ]
  • 5-(9,10-di(naphthalen-2-yl)anthracen-2-yl)-7,7-di-methyl-5,7-dihydroindeno[2,1-b]carbazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium tert-butylate; palladium diacetate; In 1,3,5-trimethyl-benzene; for 8h;Reflux; Inert atmosphere; In a three-necked flask,2-bromo-9,10-di(2-naphthyl)anthracene (0.53 g, 1.05 mmol) was added,Intermediate 2-2 (0.30 g, 1.05 mmol), potassium tert-butoxide (0.22 g, 2 mmol), palladium acetate (10 mg), S-phos (36 mg) and 30 ml1,3,5-Trimethylbenzene is heated under reflux with nitrogen for 8 hours, cooled, washed with water and dried. The crude product is purified by column chromatography to give 0.4 g of product.Product, yield, 53%
  • 19
  • [ 1257220-47-5 ]
  • 2,5-difluoro-1,4-dicyanobenzene [ No CAS ]
  • C50H34N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 20℃; for 10h;Inert atmosphere; Under nitrogen atmosphere, 0.755 g of the intermediate (E), 2.75 g of the intermediate (F), 1.40 g of potassium carbonate, 18 mL of N-methyl-2-pyrrolidinone were put into a flask and stirred at the room temperature for 10 hours. The reaction solution was added with water. The deposited solid was the organic layer was concentrated. The obtained residue was refined by silica-gel column chromatography and washed with toluene, whereby 1.60 g (yield 50%) of a yellow solid of a compound 5 was obtained.
  • 20
  • [ 1257220-47-5 ]
  • C21H16BrN [ No CAS ]
YieldReaction ConditionsOperation in experiment
48% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; for 8h; 1,1-dimethyl-1,3-dihydroindeno [2,1-b] carbazole (5.0 g, 0.018 mol) in N-bromosuccinimide (3.2 g, 0.018) in 20 mL DMF was reacted by stirring at 20 C for 8 hours. After the end of the reaction H20 added after the layer separation with ethyl acetate Column purification (n-Hexane: MC) to yield the intermediate 1-1 is 2.1 g (48%)
  • 21
  • [ 106-37-6 ]
  • [ 1257220-47-5 ]
  • [ 1361126-22-8 ]
YieldReaction ConditionsOperation in experiment
30% With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 24h; After mixing compound 10-2 15 g (53 mmol), 1,4-dibromobenzene 32 mL (265 mmol), Pd(OAc)21.2 g (5 mmol), P(t-Bu)330 mL (64 mmol), NaOt-Bu 25 g (265 mmol), and toluene 300 mL, the mixture was stirred at 120 C. for 24 hours. After completing the reaction, the mixture was cooled to room temperature, extracted with ethylacetate 1.5 L, and the obtained organic layer was washed with distilled water 400 mL. Then, solvent was removed under reduced pressure, and the obtained solid was washed with hexane, filtered, and dried. Then, the obtained product was separated using silica gel column chromatography and recrystallization to obtain compound 10-3 7 g (30%).
30% With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 24h; Compound 8-2 (15.0 g, 53.0 mmol), 1,4-dibromobenzene (32.0 mL, 265.0 mmol), Pd(OAc)2 (1.2 g, 5.0 mmol), P(t-Bu)3 (30.0 mL, 64.0 mmol), NaOt-Bu (25.0 g, 265.0 mmol), and toluene (300.0 mL) were mixed in a flask and stirred at 120C for 24 hrs. After completing the reaction, the mixture was cooled to room temperature and extracted with EA (1.5 L). The obtained organic layer was washed with distilled water (400.0 mL). The solvent was removed under reduced pressure, and the obtained solid was washed with hexane, filtered and dried. After the separation via column chromatography on silica gel and recrystallization, compound 8-3 (7.0 g, 30 %) was obtained.
30% With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 24h; 15 g (53 mmol) of compound 10-2, 32 mL (265 mmol) of 1,4-dibromobenzene, 1.2 g (5 mmol) of Pd (OAc) 2, P (t-Bu) 3 30 mL (64 mmol), 25 g (265 mmol) of NaOt-Bu and 300 mL of toluene were mixed and stirred at 120 C. for 24 h. After the reaction, the mixture was cooled to room temperature and extracted with 1.5 L of ethyl acetate. The obtained organic layer was washed with 400 mL of distilled water. Thereafter, the solvent was removed under reduced pressure, and the obtained solid was washed with hexane, filtered, and dried. Silica gel column chromatography and recrystallization to give a compound 10-3 7 g (30%).
With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 105℃; for 24h;Inert atmosphere; In a 250-mL three-necked flask, add 0.01 mol of intermediate II-a, 0.012 mol of raw material Z1, and 150 mL of toluene under nitrogen protection, and then add 6 × 10-5mol Pd2 (dba) 3, 6 × 10. -5mol triphenylphosphine, 0.03mol sodium tert-butoxide, heated to 105 C, and reacted for 24 hours under reflux. The sampling plate showed no bromide remaining and the reaction was complete; naturally cooled to room temperature, filtered, and the filtrate was spun to no fractions. The residue was passed through a neutral silica gel column to obtain intermediate b1

  • 22
  • [ 152583-10-3 ]
  • [ 1257220-47-5 ]
  • 10-benzo[h]quinolin-10-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With copper(l) iodide; potassium carbonate; 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione; In N,N-dimethyl-formamide; at 100℃; for 60h;Inert atmosphere; Firstly the 30g (116mmol) of the 10-bromobenzo[h]quinoline, 32g (116mmol) the <strong>[1257220-47-5]12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene</strong>, 32g (232mmol) the potassium carbonate, 2.6g (11.6mmol) of 1,3-bis(2-pyridyl)propane-1,3-dioneand 2.2 (11.6mmol) copper iodide filled with 1000 ml of in DMF. Degassing the solution, using N2saturated, and the heating to 100 C60h. Subsequently, adding water and toluene, the phase separation, the organic phase is washed with water two times and after Na2SO4drying, rotary evaporation and the concentrated. The crude product is filtered through silica gel with toluene, the remaining residue from the heptane/toluene recrystallization and the final sublimation under high vacuum. The purity is 99.9%. The yield is 37g (theoretical 71%).
  • 23
  • [ 1257220-47-5 ]
  • [ 2915-16-4 ]
  • C37H27N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With tri-tert-butyl phosphine; palladium diacetate; In para-xylene; for 16h;Reflux; 22 g (79.8 mmol) Of 2,12- dimethyl-10-phenyl -10,12- dihydro-10-aza-indeno - [2,1-b] fluorene,34 g (87 mmol)Of the triazine, and 15.9 ml (15.9 mmol)1 mol / l tree -tert- butylphosphine,tri1.79 g (7.9 mmol)The palladium acetateProtective-p- xylene was suspended in 120 ml of gas under.The reaction mixture was heated for 16 hours under reflux. After cooling, the organic phase was separated off, washed three times with 200 ml of water and evaporated to dryness.The residue was extracted with toluene of high temperature, which was recrystallized from toluene, and finally sublimation at high vacuum.The purity is 99.9%.Yield: 38 g (64 mmol), 80% of the theoretical value.Similarly, the following compounds were obtained
  • 24
  • [ 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%.
  • 25
  • [ 1257220-47-5 ]
  • C30H18Br2 [ No CAS ]
  • C72H50N2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; for 8h;Reflux; Inert atmosphere; In a 250 mL three-necked flask,Followed by adding M4 0.538 g,M8 0.594g,Pd2 (dba) 3 0.0916 g,Sphos 0.123g,TBuONa 0.385g and solvent toluene 50mL,N2 charge and discharge 3 times,Heating up to reflux,After 8 h reaction, the reaction was stopped,Spin dry.Using a n-hexane: dichloromethane 4: 1 as eluant, the column yielded 0.47 g (50%) of the desired solid product.
  • 26
  • [ 1257220-47-5 ]
  • 2-chloro-4,6-diphenylpyrimidine-5-carbonitrile [ No CAS ]
  • C38H26N4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% 60% sodium hydride (0.88 g, 22 mmol) and 30 mL of dehydrated dimethylformamide were added to a nitrogen-purged flask, " To the compound N (5.66 g, 20 mmol) was added 80 mL of dimethylformamide to dissolve, 10 minutes. After completion of the dropwise addition, stirring was continued for 30 minutes. 60 mL of dimethylformamide was added to and dissolved in the compound represented by the formula (C) (6.12 g, 21 mmol), followed by dropwise addition in the flask for 30 minutes. After completion of the dropwise addition, stirring was continued for 4 hours. Thereafter, 0.4 L of water was added, and crystals precipitated were collected by filtration. The crystals collected by filtration were dispersed in ethanol, stirred for one day, filtered and vacuum dried to obtain 7.54 g (14.0 mmol, 70% yield) of the compound (167).
  • 27
  • [ 3988-03-2 ]
  • [ 1257220-47-5 ]
  • C55H40N2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine; sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Reflux; 250ml of four bottles, in the atmosphere of nitrogen,0.01 mol of 4,4'-dibromobenzophenone was added,0.025 mol of intermediate D, 0.03 mol of sodium tert-butoxide,1 x 10-4 mol Pd2 (dba) 3, 1 x 10-4 mol tri-tert-butylphosphine,150 ml of toluene, heated to reflux for 24 hours,Sampling point plate, the reaction is complete.Natural cooling, filtration, the filtrate steamed, silica gel column, the target product, purity 98.8%, the yield of 68%.
  • 28
  • [ 1073-06-9 ]
  • [ 1257220-47-5 ]
  • [ 1369587-63-2 ]
YieldReaction ConditionsOperation in experiment
66% With potassium phosphate; In N,N-dimethyl acetamide; for 14h;Reflux; Example 4a Synthesis of 10-(3-bromophenyl)-<strong>[1257220-47-5]12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene</strong> 150.0 g (526 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene [1257220-47-5], 184.0 g (1.05 mmol) of 1-bromo-3-fluorobenzene [1073-06-9] and 334.7 g (1.58 mol) of potassium phosphate are initially introduced in 2 l of dimethylacetamide and heated under reflux for 14 hours. After cooling to room temperature, the solvent is removed as far as possible in a rotary evaporator, leaving a dark-brown oil. After vigorous rubbing of the flask wall with a glass rod, the product can be precipitated by slowly stirring in about 750 ml of ethanol. The solid formed is filtered off with suction, washed four times with 250 ml of ethanol each time, dried in vacuo and finally subjected to fractional sublimation at a pressure of about 10-5 mbar and 220 C., leaving 152.2 g (347 mmol, 66% of theory) of the product as a yellow glass-like solid having a purity of about 99% according to 1H-NMR.
  • 29
  • [ 1257220-47-5 ]
  • C21H11ClN2S [ No CAS ]
  • C42H27N3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine; In toluene; for 24h;Reflux; Compound 1-3-2 3.7 g (10.2 mM), <strong>[1257220-47-5]7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole</strong> 3.5g(12.2mM), Pd (OAc) 2 114 mg (0.51 mM) of PCy3, 286 mg (1.02 mM) of PCy3 and 1.96 g (20.4 mM) of NaOt-Bu were dissolved in 100 mL of toluene and refluxed for 24 hours. half After completion of the reaction, distilled water and DCM were added at room temperature. The organic layer was dried over MgSO 4, Respectively. The reaction product was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to obtain the desired compound 31 4.9 g (80%) was obtained.
  • 30
  • [ 591-18-4 ]
  • [ 1257220-47-5 ]
  • [ 1369587-63-2 ]
YieldReaction ConditionsOperation in experiment
71% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Inert atmosphere; Reflux; To the reaction flask was added Intermediate 18-4 (10g, 35.3mmol), m-bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium acetate (0.3g, 1.3mmol), tri-tert-butylphosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150 mL), under nitrogen was heated at reflux for 24 hours, cooled, toluene was removed, dichloromethane was added, washed with water, dried, the crude product by column to give 11g product, yield 71%.
71% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask was added 5,7-dihydro-7,7-dimethyl-indolo[2,1-b]carbazole (10 g, 35.3 mmol), m-bromoiodobenzene (12 g, 42 mmol) , potassium tert-butoxide (7.9 g, 70.6 mmol), palladium acetate (0.3 g), tri-tert-butylphosphine tetrafluoroborate (0.8 g) and toluene (150 mL), heated under reflux for 24 hours under nitrogen and cooled. Remove toluene, add dichloromethane, wash with water,Dry and the crude product was passed through a column to give 11 g of product, yield 71%.
71% With potassium tert-butylate; palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Reflux; Inert atmosphere; To the reaction flask was added 5,7-dihydro-7,7-dimethyl-indolo[2,1-b]carbazole (10 g, 35.3 mmol),M-bromoiodobenzene (12 g, 42 mmol), potassium t-butoxide (7.9 g, 70.6 mmol), palladium acetate (0.3 g),Tri-tert-butylphosphine tetrafluoroborate(0.8g) and toluene (150mL), heated under reflux for 24 hours under nitrogen, cooled, toluene removed,Add dichloromethane, wash with water, dry, and pass the crude product through the column.11 g of product was obtained in a yield of 71%.
  • 31
  • [ 1194-02-1 ]
  • [ 1257220-47-5 ]
  • C28H20N2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With sodium hydride; In N,N-dimethyl-formamide; at 20℃; for 10h;Inert atmosphere; To the flask was added 7,7-dimethyl-5H-indeno [2,1-b] carbazole (15 g, 53 mmol)p-fluorobenzonitrile (6.5 g, 53 mmol) and N, N-dimethylformamide (100 mL), sodium hydride (1.5 g, 64 mmol) was slowly added and reacted at room temperature for 10 hours under nitrogen. Water, extracted with dichloromethane, dried and concentrated. The crude product was purified by column chromatography to give 13 g, 65% yield.
  • 32
  • [ 1257220-47-5 ]
  • C16H10Br2N2O2 [ No CAS ]
  • C58H42N4O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
64.58% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 20h;Inert atmosphere; Reflux; In the 250ml three-necked bottle,Under nitrogen protection,0.01 mol of compound 1 was added,0.03 mol of compound M04,0.03 mol of sodium tert-butoxide,1 x 10-4 mol Pd2 (dba) 3,1 x 10-4 mol of tri-tert-butylphosphine,100 ml of toluene,Heated to reflux for 20 hours,Sampling point plate,The reaction is complete;Natural cooling,Filtration, filtrate steaming,Column chromatography to obtain the target product,HPLC purity 99.1%Yield 64.58%.
  • 33
  • [ 22439-61-8 ]
  • [ 1257220-47-5 ]
  • C33H23NS [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With potassium phosphate; copper(l) iodide; (S,S)-1,2-diaminocyclohexane; In 1,4-dioxane; for 24h;Reflux; 2-bromodibenzo [b, d] thiophene 5.0g (19.0 mM), 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole4.5 g (15.8 mM), CuI 3.0g (15.8 mM),Trans-1,2-diaminocyclohexane1.9 mL (15.8 mM)And 3.3 g (31.6 mM) of K3PO4 Dioxane and then refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added at room temperature and extracted. The organic layer was dried with MgSO 4 and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to obtain 7.3 g (85%) of the target compound 8-2.
85% With potassium phosphate; copper(l) iodide; (S,S)-1,2-diaminocyclohexane; In 1,4-dioxane; for 24h;Reflux; 1) Preparation of compound 10-2 5.0 g (19.0 mmol) of 2-bromodibenzo [b, d] thiophene, 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole 4.5 g (15.8 mmol) of CuI 3.0g (15.8 mmol), Trans-1, 2-diaminocyclohexane (1.9 mL, 15.8 mmol) and 3.3 g (31.6 mmol) of K3PO4 was dissolved in 100 mL of 1,4-oxalic acid and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added at room temperature and extracted. The organic layer was dried with MgSO 4 and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM: Hex = 1: 3) and recrystallized from methanol to obtain 7.3 g (85%) of the target compound 10-2.
  • 34
  • [ 1257220-47-5 ]
  • [ 1403604-87-4 ]
  • C34H23N3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% compound 7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole14.9 g (52.7 mmol) of1.39 g (57.9 mmol) of NaH andDMF (200 mL) was added and replaced with nitrogen.After 1 hour reaction at room temperature, Comparative Compound 2-1 (Ref 2-1)15 g (57.9 mmol) of triethylamine were added and the mixture was refluxed for 12 hours. Distilled water,Extraction was carried out using dichloromethane and NaCl.The organic layer was dried over anhydrous MgSO 4, and the solvent was removed using a rotary evaporator. The solvent was then purified by column chromatography using dichloromethane: ethyl acetate = 10: 1 to obtain 19.1 g (72%) of the objective comparative compound 6 (Ref 6).
  • 35
  • [ 1257220-47-5 ]
  • [ 1465269-57-1 ]
  • C33H22N4S [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With potassium phosphate; copper(l) iodide; rac-diaminocyclohexane; In 1,4-dioxane; for 12h;Inert atmosphere; Reflux; Compound 1-1 (6 g, 19.7 mmol)7,7-dimethyl-5,7-dihydroindeno [2,1-b] carbazole 4.3 g (15.2 mmol) of2.89 g (15.2 mmol) of CuI, 6.44 g (30.3 mmol) of K3PO4,1.82 mL (15.2 mmol) of 1,2-cyclohexanediamine and 60 mL of 1,4-dioxane were placed and replaced with nitrogen.After refluxing for 12 hours, distilled water,Extraction was carried out using dichloromethane and NaCl. The organic layer was dried over anhydrous MgSO 4, and the solvent was removed using a rotary evaporator. The solvent was then filtered through silica gel using hexane: ethyl acetate = 5: 1 to obtain 7.8 g (78%) of the desired compound 44.
 

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