19616-28-5|Bis(2,4-dimethylphenyl)amine| Ambeed

Size	Price	VIP Price	US Stock	Global Stock	In Stock
{[ item.pr_size ]}		Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}

US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days

{[ item.pr_size ]}

In Stock

- +

Please Login or Create an Account to: See VIP prices and availability

US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks

Quality Control of [ 19616-28-5 ] Purity: 97% SDS Specification

COA

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

NMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

CNMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

HPLC

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

LC-MS

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

1-2 Day Shipping
High Quality
Technical Support

Product Details of [ 19616-28-5 ]

CAS No. :	19616-28-5
Formula :	C₁₆H₁₉N
M.W :	225.33
SMILES Code :	CC1=CC=C(NC2=CC=C(C)C=C2C)C(C)=C1
MDL No. :	MFCD16619146
InChI Key :	MAINCNYZMOMWRA-UHFFFAOYSA-N
Pubchem ID :	21989085

Safety of [ 19616-28-5 ]

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

Computational Chemistry of [ 19616-28-5 ] Show Less

Physicochemical Properties

Num. heavy atoms	17
Num. arom. heavy atoms	12
Fraction Csp3	0.25
Num. rotatable bonds	2
Num. H-bond acceptors	0.0
Num. H-bond donors	1.0
Molar Refractivity	75.85
TPSA ? Topological Polar Surface Area: Calculated from Ertl P. et al. 2000 J. Med. Chem.	12.03 Å²

Lipophilicity

Log P_o/w (iLOGP)? iLOGP: in-house physics-based method implemented from Daina A et al. 2014 J. Chem. Inf. Model.	3.23
Log P_o/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry	4.92
Log P_o/w (WLOGP)? WLOGP: Atomistic method implemented from Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.	4.66
Log P_o/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.	4.38
Log P_o/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	4.7
Consensus Log P_o/w? Consensus Log P_o/w: Average of all five predictions	4.38

Water Solubility

Log S (ESOL):? ESOL: Topological method implemented from Delaney JS. 2004 J. Chem. Inf. Model.	-4.73
Solubility	0.00422 mg/ml ; 0.0000188 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Moderately soluble
Log S (Ali)? Ali: Topological method implemented from Ali J. et al. 2012 J. Chem. Inf. Model.	-4.91
Solubility	0.00278 mg/ml ; 0.0000123 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	-6.52
Solubility	0.0000677 mg/ml ; 0.000000301 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	Yes
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) and tested on 415 molecules (test set) 10-fold CV: ACC=0.72 / AUC=0.77 External: ACC=0.88 / AUC=0.94	No
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.83 / AUC=0.90 External: ACC=0.84 / AUC=0.91	Yes
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.80 / AUC=0.86 External: ACC=0.80 / AUC=0.87	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	Yes
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) and tested on 2579 molecules (test set) 10-fold CV: ACC=0.77 / AUC=0.85 External: ACC=0.78 / AUC=0.86	No
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from Potts RO and Guy RH. 1992 Pharm. Res.	-4.18 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	1.0
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<2.0
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties, trained on 12'782'590 molecules and tested on 40 external molecules (r² = 0.94)	1.99

Application In Synthesis of [ 19616-28-5 ]

* 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 [ 19616-28-5 ]

[ 19616-28-5 ] Synthesis Path-Downstream 1~35

1
[ 35523-91-2 ]
[ 19616-28-5 ]

References: [1]Helvetica Chimica Acta,1924,vol. 7,p. 116.

2
[ 50-00-0 ]
[ 19616-28-5 ]
[ 67-64-1 ]
1-(2,4-dimethyl-phenyl)-4,6,8-trimethyl-quinolinium; perchlorate [ No CAS ]

References: [1]Zhurnal Obshchei Khimii,1959,vol. 29,p. 3050; engl. Ausg. S. 3015.

3
[ 105-67-9 ]
[ 19616-28-5 ]
[ 95-68-1 ]

References: [1]Chemische Berichte,1887,vol. 20,p. 1040.

4
[ 19616-28-5 ]
[ 123-63-7 ]
1-(2,4-dimethyl-phenyl)-2,4,6,8-tetramethyl-quinolinium; perchlorate [ No CAS ]

References: [1]Zhurnal Obshchei Khimii,1959,vol. 29,p. 3802; engl. Ausg. S. 3764.

5
[ 19616-28-5 ]
[ 55389-77-0 ]

References: [1]Bulletin de la Societe Chimique de France,1974,p. 2960 - 2962.

6
[ 583-70-0 ]
[ 2050-43-3 ]
[ 19616-28-5 ]

References: [1]Journal of the Chemical Society C: Organic,1968,p. 2244 - 2247.

7
[ 35523-91-2 ]
[ 7664-93-9 ]
[ 31058-43-2 ]
[ 615-90-7 ]
[ 19616-28-5 ]
[ 105-67-9 ]

References: [1]Helvetica Chimica Acta,1924,vol. 7,p. 116.

9
[ 955107-51-4 ]
[ 19616-28-5 ]
C₅₈H₅₄N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃;	In a stream of argon, 4 g (10 mmol) of) 1,2-bis(4-(4'-chlorophenyl)phenyl)ethene, 5.6 g (25 mmol) of <strong>[19616-28-5]bis(2,4-dimethylphenyl)amine</strong>, 0.03 g (1.5 mol percent) of palladiumacetate, 0.06 g (3 mol percent) of tri-t-butylphosphine, 2.4 g (25 mmol) of t-butoxysodium, and 100 mL of dry toluene were added to a 300-mL three-necked flask provided with a cooling pipe, and then the whole was stirred under heat at 100° C. overnight. After the completion of the reaction, the precipitated crystal was taken by filtration, and was washed with 50 mL of toluene and 100 mL of methanol, whereby 6.6 g of a pale yellow powder were obtained. The powder was identified as Compound (D-2-2) (in 85percent yield) by 1H-NMR spectroscopy (FIG. 1) and FD-MS. It should be noted that the 1H-NMR spectrum of the compound was measured by using a DRX-500 (heavy methylene chloride solvent) manufactured by Brucker. The maximum absorption wavelength and maximum fluorescence wavelength of the resultant compound measured in a toluene solution were 383 nm and 441 nm, respectively.

References: [1]Patent: US2008/4445,2008,A1 .Location in patent: Page/Page column 63.

10
[ 955107-58-1 ]
[ 19616-28-5 ]
C₆₀H₄₂N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃;	In a stream of argon, 4.1 g (10 mmol) of 4-bromo-4' (p-bromophenyl)-(E)-1,2-stilbene, 5.4 g (25 mmol) of bis(2-naphthyl)amine, 0.03 g (1.5 mol percent) of palladium acetate, 0.06 g (3 mol percent) of tri-t-butylphosphine, 2.4 g (25 mmol) of t-butoxysodium, and 100 mL of dry toluene were added to a 300-mL three-necked flask provided with a cooling pipe, and then the whole was stirred under heat at 100° C. overnight. After the completion of the reaction, the precipitated crystal was taken by filtration, and was washed with 50 mL of toluene and 100 mL of methanol, whereby 7.1 g of a pale yellow powder were obtained. The powder was identified as Compound (D-4-4) (in 90percent yield) by FD-MS. The maximum absorption wavelength and maximum fluorescence wavelength of the resultant compound measured in a toluene solution were 397 nm and 446 nm, respectively. The emission spectrum is shown in FIG. 2.

References: [1]Patent: US2008/4445,2008,A1 .Location in patent: Page/Page column 63.

11
[ 19616-28-5 ]
[ 55389-81-6 ]

References: [1]Bulletin de la Societe Chimique de France,1974,p. 2960 - 2962.

12
[ 92-66-0 ]
[ 19616-28-5 ]
[ 230313-56-1 ]

References: [1]European Journal of Organic Chemistry,2010,p. 6824 - 6830.

13
[ 19616-28-5 ]
[ 1336947-41-1 ]

Yield	Reaction Conditions	Operation in experiment
		Example 2 Synthesis of N,N,N',N'-tetrakis(2,4-dimethylphenyl)-9,9'-spiro-bifluorene-2,7-diamine (HTM2) The synthesis is carried out analogously to Example 1, with the difference that 118.7 g of <strong>[19616-28-5]di(2,4-dimethylphenyl)amine</strong> (Wie-Flex Technology) are employed instead of the di-p-tolylamine. After crystallisation six times from dioxane and sublimation (10-5 mbar, 350° C.), 72 g (93 mmol, 45percent) of N,N,N',N'-tetrakis(2,4-dimethylphenyl)-9,9'-spirobifluorene-2,7-diamine (HTM2) are obtained as a colourless solid. Analytical data: Tg (DSC) 128° C., purity >99.98percent.

References: [1]Patent: US2013/15403,2013,A1 .Location in patent: Page/Page column.

14
[ 27973-29-1 ]
[ 19616-28-5 ]
N,N,N',N'-tetrakis-(2,4-dimethylphenyl)pyrene-1,6-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; toluene; for 12h;Inert atmosphere; Reflux;	19.08 g (0.053 mol) of 1 ,6-dibromopyrene and 27.0 g (0.12 mol) of N-(2,4- dimethylphenyl)-2,4-dimethylphenylamine (Miguel Angel Chem Taiwan) are dissolved in 500 ml of xylene and degassed. 0.15 ml (0.66 mmol / 1 M soln. in toluene) of tri-tert-butylphosphine, 15.61 g (0.162 mol) of NaOtBu and 89.44 mg (0.398 mmol) of Pd(OAc)2 are added, and the mixture is degassed again and heated under reflux for 12 h. When the reaction is complete, the warm mixture is filtered through aluminium oxide B (activity grade 1), washed with water, dried and evaporated. The residue is purified by Soxhlet extraction with toluene / heptane (1 :1) and crystallised from toluene. The content of product according to HPLC is 98percent with an overall yield of 14.8 g (43percent).

References: [1]Patent: WO2013/185871,2013,A1 .Location in patent: Page/Page column 25; 26.

15
[ 19616-28-5 ]
[ 90-13-1 ]
[ 1609171-46-1 ]

References: [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1391 - 1394.
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1391 - 1394.

16
[ 90-11-9 ]
[ 19616-28-5 ]
[ 1609171-46-1 ]

References: [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1391 - 1394.
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 1391 - 1394.

17
[ 591-50-4 ]
[ 19616-28-5 ]
[ 159946-78-8 ]

Yield	Reaction Conditions	Operation in experiment
98.6%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 120℃; for 16h;Inert atmosphere;	[136] N-(2,4-dimethylphenyl)-2,4-dimethyl-N-phenylaniline (Compound 15): A mixture of <strong>[19616-28-5]bis(2,4-dimethylphenyl)amine</strong> (Compound 14) (9.4 g, 41 .8 mmol), iodobenzene (17.14 g, 84 mmol), Pd(OAc)2 (0.47 g, 2.1 mmol), P(t-Bu)3 (0.848 g, 4.2 mmol), sodium tert-butoxide (7.68 g, 80 mmol) in toluene (120 mL) was degassed and heated at 120°C for 16 hours. The resulting mixture was poured into ethyl acetate (250 mL), washed with brine, dried over Na2S04, loaded on silicagel and purified by flash column using eluent of hexanes. After removal of solvent, an oil (Compound 15) was obtained (12.4 g, in 98.6percent yield).

References: [1]Patent: WO2014/93353,2014,A1 .Location in patent: Paragraph 136.

18
[ 19616-28-5 ]
[ 519180-54-2 ]

References: [1]Patent: WO2014/93353,2014,A1 .

19
[ 19616-28-5 ]
[ 1613149-62-4 ]

References: [1]Patent: WO2014/93353,2014,A1 .

20
[ 19616-28-5 ]
[ 1613149-63-5 ]

References: [1]Patent: WO2014/93353,2014,A1 .

21
[ 19616-28-5 ]
[ 1613149-53-3 ]

References: [1]Patent: WO2014/93353,2014,A1 .

22
[ 583-70-0 ]
[ 95-68-1 ]
[ 19616-28-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	2,4-dimethylaniline 2.67 g (molecular weight 121,22 mmol) was added to a 100 ml reaction flask under nitrogen.2.68 g of 2,4-dimethylbromobenzene (molecular weight 184,20 mmol), 5.76 g of sodium tert-butoxide (molecular weight 96,60 mmol),Pd2(dba)3 183 mg (molecular weight 916, 0.2 mmol), P(tBu)3 121 mg (molecular weight 202, 0.6 mmol).Anhydrous toluene 50 ml.After the addition, the oil bath was slowly heated to reflux reaction, and the reaction end was monitored by TLC, and the reaction was completed in 10 hours.Cooled, quenched with water, extracted with 50ml of dichloromethane, the organic phase dried over anhydrous MgSO4, the organic phase evaporated to dryness,The resulting solid was separated by column chromatography to give a white solid 3.8g, molecular weight 225, 85percent yield.
85%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	2,4-dimethylaniline 2.67 g (molecular weight 121,22 mmol) was added to a 100 ml reaction flask under nitrogen.2.68 g of 2,4-dimethylbromobenzene (molecular weight 184,20 mmol), 5.76 g of sodium tert-butoxide (molecular weight 96,60 mmol),Pd2(dba)3 183 mg (molecular weight 916, 0.2 mmol), P(tBu)3 121 mg (molecular weight 202, 0.6 mmol).Anhydrous toluene 50 ml. After the addition, the oil bath was slowly heated to reflux reaction, and the reaction end was monitored by TLC, and the reaction was completed in 10 hours. coldThe reaction was quenched with water, extracted with 50 mL of dichloromethaneThe organic phase was evaporated to dryness, resulting solid was purified by column chromatography to give 3.8g white solid,Molecular weight 225, yield 85percent.
85%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	Under the protection of nitrogen, in 100 ml reaction flask is added 2,4-dimethylaniline 2.67 g (molecular weight 121,22 mmol), 2,4-dimethylbromo benzene 3.68 g (molecular weight 184, 20 mmol), sodium tert-5.76 g (molecular weight 96, 60 mmol), Pd2 (dba) 3 183 mg (molecular weight 916, 0.2 mmol), P (tBu) 3 121 mg (molecular weight 202, 0.6 mmol). Anhydrous toluene 50 ml. Canada finishes, the oil bath to be slowly heated to reflux reaction, TLC monitoring end point of the reaction, 10 hours of reaction. The cooling, water quenching reaction, for 50 ml dichloromethane extraction, the organic phase with anhydrous MgSO4 drying, the organic phase to dryness, the resulting solid method for the chromatographic separation, to obtain 3.8 g white solid, molecular weight 225, yield 85percent.

84%	With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; sodium t-butanolate; In toluene; at 100℃;Inert atmosphere;	[135] Bis(2,4-dimethylphenyl)amine (Compound 14): A mixture of 2,4- dimethylaniline (6.05 g, 50 mmol), 2,4-dimethylbromobenzene (9.25 g, 50 mmol), Pd(dppf)CI2 (0.88 g, 1 .2 mmol), sodium tert-butoxide (KOBu') (9.6 g, 0.1 mmol) in toluene (120 mL) was degassed and heated at 100°C overnight. The resulting mixture was worked up with dichloromethane/brine, dried over Na2S04, loaded on silica gel and purified by flash column using eluents of hexanes to hexanes/dichloromethane 9:1 . After removal of solvent, a liquid was obtained (9.45 g, in 84percent yield).
77%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 20℃; for 40h;	a. Synthesis of 2,2?,4,4?-tetramethyldiphenylamine (Intermediate 3). 10336] To 6.0 g of 2,4-dimethylaniline, 8.7 g of 1-bromo-2,4-dimethylbenzene, 916 mg of Pd2(dba)3, and 404 mg of P(t-13u)3 in 400 mE toluene was added 5.29 g of sodium tert-butoxide. The reaction was stirred at room temperature. After 40 hours, water and brine were added. The toluene layer was separated and the aqueous layer was extracted with dichloromethane. The organic layers were combined, dried over sodium sulfate, and concentrated by rotary evaporation. The crude material was purified by MPEC on silica gel eluting with 95:5 to 80:20 hexanes:dichloromethane, combining the purest fractions to give, after concentration by rotary evaporation, Intermediate 3 (8.7 g, 77percent yield) as a colorless liquid.
57%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 5h;Inert atmosphere; Reflux;	Add 2,4-dimethylbromobenzene to a 500 mL three-necked flask equipped with magnetic stirring at room temperature.2,4-Dimethylaniline, Pd2(dba)3, tri-tert-butylphosphine, sodium t-butoxide, toluene.After the addition, the nitrogen gas was replaced 3 times, the stirring was started, and the oil bath was heated and heated to reflux for 5 hours.The TLC tracking reaction showed that the two starting materials were completely reacted (PE/EA = 20:1, product Rf = 0.8) and the reaction was stopped. The reaction solution was cooled to room temperature, stirred for 10 minutes with pure water, separated, and the aqueous phase was extracted with toluene, and the toluene phase was combined and saturated.Washed with brine, dried over anhydrous sodium sulfate, filtered and evaporatedDilute the crude product with as little petroleum ether as possible: dichloromethane = 10:1, and place the liquid on a silica gel column.Keep the polarity of the eluent unchanged with petroleum ether: dichloromethane = 10:1 until the product is rinsed.Dry under reduced pressure to give an off-white solid.Recrystallization from n-hexane gave 13 g of a white crystalline solid.HPLC 99.18percent, yield 57percent.
3.8 g	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	Under the protection of nitrogen,Add in a 100ml reaction bottle2.67 g of 2,4-dimethylaniline (molecular weight: 121, 22 mmol),2.68 g of 2,4-dimethylbromobenzene (molecular weight 184, 20 mmol),5.76 g of sodium tert-butoxide (molecular weight 96,60 mmol),Pd2(dba)3 183mg (molecular weight 916, 0.2mmol),P(tBu)3 121 mg (molecular weight 202, 0.6 mmol).Anhydrous toluene 50 ml. Plus,The oil bath is slowly heated to reflux reaction.TLC monitors the end of the reaction,The reaction was completed in 10 hours.Cool, add water to quench the reaction,Extracted with 50 ml of dichloromethane,The organic phase was dried over anhydrous MgSO4.The organic phase is evaporated to dryness.The obtained solid is separated by column chromatography.3.8 g of a white solid,Molecular weight 225, yield 85percent by weight.

References: [1]Patent: CN108727366,2018,A .Location in patent: Paragraph 0071; 0072; 0073; 0074; 0075.
[2]Patent: CN109134457,2019,A .Location in patent: Paragraph 0083-0087.
[3]Patent: CN109134458,2019,A .Location in patent: Paragraph 0055; 0056; 0057; 0058; 0059.
[4]Patent: WO2014/93353,2014,A1 .Location in patent: Paragraph 135.
[5]Patent: US2017/29362,2017,A1 .Location in patent: Paragraph 0336.
[6]ACS Catalysis,2014,vol. 4,p. 3470 - 3480.
[7]Patent: CN109665935,2019,A .Location in patent: Paragraph 0051; 0053; 0054; 0055.
[8]Patent: CN109134456,2019,A .Location in patent: Paragraph 0086; 0087; 0088; 0089.

23
[ 19616-28-5 ]
1,2-benzo-3,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene [ No CAS ]
C₆₀H₅₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; n-hexyllithium; palladium diacetate; In hexane; toluene; for 1h;Reflux;	Hexyllithium (2.5 M in hexane, 1.2 eq.) is added dropwise to a solution of <strong>[19616-28-5]bis(2,4-dimethylphenyl)amine</strong> (1.25 eq), 1,2-benzo-3-bromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene (1 eq), Pd(OAc)2 (0.02 eq) and 2-(dicyclohexylphosphino)-2?,6?-dimethoxy)biphenyl (S-Phos, 0.04 eq) in toluene, and the mixture is subsequently heated under reflux for 1 h. After cooling to room temperature, water is added, the organic phase is separated off, dried using MgSO4 and filtered through silica gel. The solvent is removed, and the residue is washed with acetonitrile and isopropanol. Yield: 90percent; purity; 99.2percent (HPLC). The purity can be increased to 99.95percent by Soxhlett extraction and sublimation. [0122] Further Examples with Hexyllithium or LDA as Base:

References: [1]Patent: US2014/309458,2014,A1 .Location in patent: Paragraph 0121-0122.

24
[ 19616-28-5 ]
[ 1001911-28-9 ]
C₄₄H₄₁N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With tri-tert-butyl phosphine; n-hexyllithium; palladium diacetate; In hexane; toluene; for 1h;Reflux;	Hexyllithium (2.5 M in hexane, 1.2 eq.) is added dropwise to a solution of <strong>[19616-28-5]bis(2,4-dimethylphenyl)amine</strong> (1.25 eq), 1,2-benzo-3-bromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene (1 eq), Pd(OAc)2 (0.02 eq) and 2-(dicyclohexylphosphino)-2?,6?-dimethoxy)biphenyl (S-Phos, 0.04 eq) in toluene, and the mixture is subsequently heated under reflux for 1 h. After cooling to room temperature, water is added, the organic phase is separated off, dried using MgSO4 and filtered through silica gel. The solvent is removed, and the residue is washed with acetonitrile and isopropanol. Yield: 90percent; purity; 99.2percent (HPLC). The purity can be increased to 99.95percent by Soxhlett extraction and sublimation. [0122] Further Examples with Hexyllithium or LDA as Base:

References: [1]Patent: US2014/309458,2014,A1 .Location in patent: Paragraph 0121-0122.

25
[ 19616-28-5 ]
[ 1001911-28-9 ]
[ 865-48-5 ]
C₄₄H₄₁N [ No CAS ]
5-tert-butoxy-7,7,13,13-tetramethyl-7H,13H-benzo[g]indeno[3,2-b]fluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With di(tert-butyl)chlorophosphine; palladium diacetate; In toluene; for 2h;Reflux;	A mixture of sodium tert-butoxide (1.2 eq.), <strong>[19616-28-5]bis(2,4-dimethylphenyl)amine</strong> (1.25 eq), 1,2-benzo-3-bromo-6,6,12,12-tetramethyl-6,12-dihydroindeno-[1,2-b]fluorene (1 eq), Pd(OAc)2 (0.02 eq) and 2-(dicyclohexylphosphino)-2?,6?-dimethoxy)biphenyl (S-Phos, 0.04 eq) in toluene is heated under reflux for 2 h. After cooling to room temperature, water is added, the organic phase is separated off, dried using MgSO4 and filtered through silica gel. The solvent is removed. The 1H-NMR spectrum of the residue shows product type A: by-product type NA=17:80. [0118] Further examples with variation of ligand and starting-material type:

References: [1]Patent: US2014/309458,2014,A1 .Location in patent: Paragraph 0417-0418.

26
[ 90-11-9 ]
[ 19616-28-5 ]
[ 865-48-5 ]
[ 50337-75-2 ]
[ 1609171-46-1 ]

References: [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 1391 - 1394.

27
1,7-dibromopyrene [ No CAS ]
[ 19616-28-5 ]
C₄₈H₄₄N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
10%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 2h;Inert atmosphere; Reflux;	b. Compound 5 10337] To a mixture of 300mg of Intermediate 2 in 14 mE toluene under nitrogen atmosphere was added 5 mg of P(t-13u)3 and 46 mg of Pd2(dba)3. Next, 376 mg of Intermediate 3 and 161 mg of sodium tert-butoxide were added. The reaction was heated at reflux for 2 hours. After the reaction was cooled, water was added and the contents were extracted with dichloromethane. The combined extracts were dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The crude material was purified by MPEC on silica gel eluting with 95:5 to 75:25 hexanes:dichloromethane. Fractions containing the desired compound were combined, concentrated by rotary evaporation, then dissolved in hexanes/ethyl acetate. Afier slow evaporation of the solvents, the resulting solid was triturated with hot dichloromethane to provide Compound 5 (52 mg, 10percent yield, 99.62percent pure) as a gold-orange solid.

References: [1]Patent: US2017/29362,2017,A1 .Location in patent: Paragraph 0335; 0337.

28
[ 19616-28-5 ]
1-iodo-7-(2,2',4,4'-tetramethyldiphenylamino)pyrene [ No CAS ]

References: [1]Patent: US2017/29362,2017,A1 .

29
[ 19616-28-5 ]
C₅₈H₄₇N₃ [ No CAS ]

References: [1]Patent: US2017/29362,2017,A1 .

30
[ 19616-28-5 ]
(7-bromopyren-1-yl)trimethylsilane [ No CAS ]
1-trimethylsilyl-7-(2,2',4,4'-tetramethyldiphenylamino)pyrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 104℃; for 4h;Inert atmosphere;	c. Synthesis of 1 -Trimethylsilyl-7-(2,2?,4,4?-tetramethyldi- phenylamino)pyrene (Intermediate 8) 10355] To 5.8 g of Intermediate 7 in 80 mE toluene under nitrogen atmosphere was added 194 mg of P(t-13u)3 and 440 mg of Pd2(dba)3. Next, 4.73 g of Intermediate 3 and 2.02 g of sodium tert-butoxide were added. The reaction was heated at Tb=lO4° C. for 4 hours. Afier the reaction was cooled, water was added and the contents were extracted with dichloromethane. The combined extracts were dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The crude material was dissolved in dichloromethane and purified by MPEC eluting with 95:5 to 70:30 hexanes:dichloromethane. The less pure fractions were repurified by MPEC on silica gel, eluting with 95:5 to 80:20 hexanes:dichloromethane. The combined lots provided Intermediate 8 (7.3 g, 89percent yield) as a yellow solid.

References: [1]Patent: US2017/29362,2017,A1 .Location in patent: Paragraph 0355.

31
[ 19616-28-5 ]
2,2′-dibromo-4,4′,6,6′-tetramethyldiphenylamine [ No CAS ]