Name: 4496-49-5|4-tert-Butyl-N-phenylaniline|97%
Brand: Ambeed
SKU: A749769
Price: 26.0 USD
Availability: InStock
Rating: 99 (25 reviews)

1
[ 507-20-0 ]
[ 122-39-4 ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,1935,vol. 57,p. 195,196

2
[ 122-39-4 ]
[ 75-65-0 ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,1935,vol. 57,p. 195,196

3
[ 769-92-6 ]
[ 118-91-2 ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,1935,vol. 57,p. 195,196

4
[ 17332-56-8 ]
[ 4496-49-5 ]

Reference： [1]Journal of medicinal and pharmaceutical chemistry,1962,vol. 5,p. 54 - 63

5
[ 4496-49-5 ]
[ 114687-15-9 ]

Reference： [1]Bulletin of the Academy of Sciences of the USSR Division of Chemical Science,1990,vol. 39,p. 657 - 662
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1990,p. 743 - 749
[2]Bulletin of the Academy of Sciences of the USSR Division of Chemical Science,1990,vol. 39,p. 657 - 662
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1990,p. 743 - 749

6
[ 114687-15-9 ]
[ 4496-49-5 ]

Reference： [1]Bulletin of the Academy of Sciences of the USSR Division of Chemical Science,1990,vol. 39,p. 657 - 662
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1990,p. 743 - 749

7
[ 4496-49-5 ]
C₁₆H₁₈NO [ No CAS ]

Reference： [1]Russian Chemical Bulletin,1994,vol. 43,p. 1651 - 1656
Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation),1994,p. 1746 - 1751

8
[ 769-92-6 ]
[ 98-80-6 ]
[ 4496-49-5 ]

Reference： [1]Green Chemistry,2018,vol. 20,p. 4891 - 4900
[2]Tetrahedron Letters,1998,vol. 39,p. 2933 - 2936
[3]Tetrahedron Letters,1998,vol. 39,p. 7979 - 7982
[4]ACS Catalysis,2018,vol. 8,p. 7308 - 7325

9
[ 3972-65-4 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); C35H41P; In toluene; at 80℃; for 2h;Inert atmosphere;Product distribution / selectivity;	A flame-dried Schlenk flask was charged with tris(dibenzylideneacetone)palladium (4.6 mg, 0.005 mmol), 1 (4.4 mg, 0.025 mmol) or 6a (11.9 mg, 0.025 mmol), sodium terf-butoxide (134 mg, 1.40 mmol) and toluene (2.0 ml_) under nitrogen. Aryl bromide (1.00 mmol) and amine (1.10 mmol) were added and the resulting red solution heated at 800C with rapid stirring until reaction was complete, as judged by GC analysis. The reaction mixture was allowed to cool to room temperature, diluted with diethyl ether, passed through celite and the solvent removed to leave a yellow solid. Known products were characterised by NMR spectroscopy and mass spectrometry and unknown products by NMR spectroscopy, mass spectrometry and high resolution mass spectrometry (HRMS). The conversions were calculated using GC analysis as an average over three repeats.

Reference： [1]Journal of Organic Chemistry,2003,vol. 68,p. 452 - 459
[2]Journal of Organic Chemistry,2004,vol. 69,p. 6504 - 6506
[3]Journal of Organic Chemistry,2000,vol. 65,p. 1144 - 1157
[4]Advanced Synthesis and Catalysis,2008,vol. 350,p. 1801 - 1806
[5]Patent: WO2009/138708,2009,A1 .Location in patent: Page/Page column 19-20
[6]European Journal of Organic Chemistry,2014,vol. 2014,p. 2070 - 2076
[7]Journal of Materials Chemistry C,2018,vol. 6,p. 12355 - 12363

Yield	Reaction Conditions	Operation in experiment
75%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 95℃; for 4h;	General procedure: 4-tert-butylaniline(1.5 g, 0.010 mol) (3-bromophenyl)trimethylsilane (2.3 g, 0.010 mol), Pd(dba)2(0.5 g, 0.0005 mol), sodium-tert-butoxide(2.8 g, 0.030 mol) and 130ml toluene was added stirring at 95C for 4 hours. Reaction after H20:MC after separation (n-HEXANE: MC) column purification 1-4 intermediate that is a 2.2 g (75%) are obtained.
71%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 95℃; for 4h;	General procedure: 1,3-Diiodobenzene (3.3 g, 0.010 mol) to 3-bromo-9H-carbazole (5.4 g, 0.022 mol),Pd (dba) 2 (0.5 g, 0.0005 mol), sodium-tert-butoxide (1.9 g, 0.020 the mol) into a 100mL Toluene then it was reacted with stirring for 4 hours at 95 C. After the layer separationin the MC column purification (N-HEXANE:: MC) after the end of the reaction H20 to Intermediate 1-1 ; 3.5 g (62% yield) was obtained. (M / z = 566) 3,5-Dimethylaniline (1.2 g, 0.010 mol) for (4-bromophenyl) trimethylsilane (2.5 g,0.011 mol) and the mixture in Example 1-Preparation Example 1 in the same manner asin synthesis To give the 2.0 g (76% yield). (M / z = 269)
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 340℃;	General procedure: The bromobenzene (1.1 equiv.) Was dissolved in toluene in a round bottom flask, 4-aminobenzene-1-ylium (1 eq.), Pd2(dba)3 (0.3 equiv), 50% P (t-Bu)3 (9 eq.) It was added NaOt-Bu (3 equivalents) and stirred at 40C . When the reaction is complete to obtain a CH2Cl2 and extracted with water and then the resulting compound with diphenylamine and the organic layer was dried over MgSO4 and concentrated to silicagel column and recrystallized (yield: 96%).

	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: 4-bromo-1,1'-biphenyl (5.6g, 24mmol) was dissolved in toluene, [1,1'-biphenyl]-4-amine (3.4g, 20mmol), Pd2(dba)3 (0.5g, 0.6mmol), P(t-Bu)3 (0.2g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (300 mL) was added to each of the back, and refluxed under strring for 24 hours at 100C. After the reaction was terminated with water and extracted with ether. The organic layer was dried over MgSO4 and concentrated and to the resulting organic silicagel column and re-crystallization the final compound 6.2g (Yield 80%).
	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: To a round bottom flask Sub 1-3-1-1 (1.9g, 20mmol), Sub 1-3-2-1 (5.5g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g , 2mmol), NaOt-Bu (5.8g, 60mmol), were added to toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100C . Ether and a water extraction of organic layer after MgSO4to dry a formed after silicagel column Sub 1-3 (9) are the and recrystallization 5.2g a (yield: 64%)obtained.
	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: To a round bottom flask Sub 2-1-1 (1.9g, 20mmol), Sub 2-2-1 (5.5g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), were added to toluene (210mL), respectively, and stirred at reflux for 24 hours, 100 C thereby. The organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silica gel column and the resulting organic one was concentrated to a Sub 2-9 5.2g (yield: 64%) was obtained.
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: 4-bromo-1,1'-biphenyl (5.6 g, 24 mmol) was dissolved in toluene and then [1,1'-biphenyl] -4-amine (3.4 g, 20 mmol), Pd2 (dba) (0.2 g, 2 mmol), NaOt-Bu (5.8 g, 60 mmol) and toluene (300 mL) were added to the reaction mixture, and the mixture was refluxed at 100 C for 24 hours. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.2 g (yield: 80%) of final compound.
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	General procedure: 4-bromo-1,1'-biphenyl (5.6 g, 24 mmol) was dissolved in toluene and then [1,1'-biphenyl] -4-amine (3.4 g, 20 mmol), Pd2 (dba) (0.2 g, 2 mmol), NaOt-Bu (5.8 g, 60 mmol) and toluene (300 mL) were added to the reaction mixture, and the mixture was refluxed at 100 C for 24 hours. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.2 g (yield: 80%) of final compound.
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	General procedure: To a round bottom flask was added an amine compound (1 eq.),Bromine compound (1.1 eq.),Pd2 (dba) 3 (0.05 mol%),P (t-Bu) 3 (0.1 eq.),NaOt-Bu (3 eq.),toluene (10.5 mL / 1 mmol) is added and the reaction proceeds at 100 C.After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain product Sub 7.
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	General procedure: A round bottom flask was charged with an amine compound (1 eq), a bromine compound (1.1 eq), Pd2(dba)3 (0.05 mol%), P(t-Bu) 3 (0.1 equivalent), NaOt-Bu (3 equivalents)toluene (10.5 mL / 1 mmol) is added and the reaction proceeds at 100 C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain product Sub 7.

12
[ 769-92-6 ]
[ 2996-92-1 ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,2000,vol. 122,p. 7600 - 7601

13
[ 769-92-6 ]
[ 934-56-5 ]
[ 4496-49-5 ]

Reference： [1]Tetrahedron Letters,2002,vol. 43,p. 3091 - 3094

14
[ 3972-56-3 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Reference： [1]Dalton Transactions,2018,vol. 47,p. 8690 - 8696
[2]Angewandte Chemie - International Edition,2002,vol. 41,p. 4746 - 4748
[3]European Journal of Organic Chemistry,2014,vol. 2014,p. 2070 - 2076
[4]ChemPlusChem,2017,vol. 82,p. 750 - 757

15
[ 160788-98-7 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,2003,vol. 125,p. 6653 - 6655

16
[ 62-53-3 ]
[ 247018-51-5 ]
[ 4496-49-5 ]

Reference： [1]Journal of Organic Chemistry,2003,vol. 68,p. 9563 - 9573
[2]Journal of Organic Chemistry,2006,vol. 71,p. 430 - 433

17
[ 769-92-6 ]
[ 16668-99-8 ]
[ 4496-49-5 ]

Reference： [1]Tetrahedron,2007,vol. 63,p. 11349 - 11354

18
[ 98-54-4 ]
(CH₂O)x [ No CAS ]
[ 4496-49-5 ]

Reference： [1]Journal of Organic Chemistry,2003,vol. 68,p. 9563 - 9573

19
[ 591-50-4 ]
resin-bound 3-nitrophenylboronic acid [ No CAS ]
[ 4496-49-5 ]

Reference： [1]Journal of the American Chemical Society,2000,vol. 122,p. 7600 - 7601

20
[ 591-51-5 ]
CH₃(CH₂)3CH(C(O)Cl)CH₂CH₃ [ No CAS ]
[ 4496-49-5 ]

Reference： [1]Tetrahedron Letters,1998,vol. 39,p. 7979 - 7982

21
[ 769-92-6 ]
[ 4496-49-5 ]

Reference： [1]Journal of medicinal and pharmaceutical chemistry,1962,vol. 5,p. 54 - 63

22
[ 20330-45-4 ]
[ 4496-49-5 ]

Reference： [1]Journal of medicinal and pharmaceutical chemistry,1962,vol. 5,p. 54 - 63

23
[ 4496-49-5 ]
[ 131222-99-6 ]
C₅₀H₄₆N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃;	Under argon flow, 6,12-dibromochrysene (3.8 g, 10 mmol), 4-t-butyldiphenylamine (5.6 g, 25 mmol), palladium acetate (0.03 g, 1.5 mol %), tri-t-butylphosphine (0.06 g, 3 mol %), t-butoxysodium (2.4 g, 25 mmol), and anhydrous toluene (100 mL) were added to a 300-mL three-neck flask equipped with a condenser, and the mixture was heated overnight at 100 C. with stirring. After completion of reaction, precipitated crystals were collected through filtration, followed by washing with toluene (50 mL) and methanol (100 mL), to thereby yield 5.3 g of a pale yellow powder. The powder was identified as compound (10) through an NMR spectrum (see FIG. 7) and an FD-MS (yield: 79%). The NMR spectrum was obtained under the same conditions as employed in Synthesis Example 1.

Reference： [1]Patent: US2006/52641,2006,A1 .Location in patent: Page/Page column 4; 11

24
[ 27973-29-1 ]
[ 4496-49-5 ]
C₄₈H₄₄N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃;	Under an argon gas flow, 3.6 g (10 mmol) of 1,6-dibromopyrene, 5.6 g (25 mmol) of 4-t-butyl diphenyl amine, 0.03 g (1.5 mol%) of palladium acetate, 0.06 g (3 mol%) of tri-t-butyl phosphine, 2.4 g (25 mmol) of t-butoxy sodium and 100 milliliter of dried toluene were charged into a three-necked flask having a capacity of 300 milliliter and equipped with a condenser, and then stirred under heating at a temperature of 100C over night. After completion of the reaction, the precipitated crystals were separated from the reaction solution by filtration, and then washed with 50 milliliter of toluene and 100 milliliter of methanol, thereby obtaining 5.1 g of a light-yellow powder. The thus obtained powder was subjected to NMR spectrum analysis (Fig. 2) and FD-MS. As a result, the reaction product was identified as Compound (9) (yield: 79%). Meanwhile, the NMR spectrum was measured by the same method as described in SYNTHESIS EXAMPLE 1.

Reference： [1]Journal of Organic Chemistry,2009,vol. 74,p. 8472 - 8475
[2]Patent: EP1604974,2005,A1 .Location in patent: Page/Page column 18; 19

25
[ 167218-29-3 ]
[ 4496-49-5 ]
C₃₆H₃₄N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper; potassium carbonate; In dodecane; at 200 - 212℃; for 15h;	There were mixed 20.70 g (0.050 mole) of N-(4'-iodobiphenylyl)acetanilide, 13.50 g (0.060 mole) of <strong>[4496-49-5]4-tert-butyldiphenylamine</strong>, 10.40 g (0.075 mole) of anhydrous potassium carbonate, 0.20 g (0.003 mole) of copper powder and 10 ml of n-dodecane, followed by reaction at 200 to 212C for 15 hours. The reaction product was extracted with 200 ml of toluene, and the insoluble matter was removed by filtration. Then, the filtrate was concentrated to obtain oily matter. The oily matter was dissolved in 80 ml of isoamyl alcohol, and 5 ml of water and 5.00 g (0.075 mole) of 85% potassium hydroxide were added, followed by hydrolysis at 130C. After isoamyl alcohol was removed by steam distillation, extraction with 250 ml of toluene was performed, and the organic layer was washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier: silica gel, eluate: toluene/n-hexane=1/2) to obtain 18.8 g (yield: 73.5%, HPLC purity: 98.0%) of N-(4-text-butylphenyl)-N,N'-diphenyl-4,4'-diaminobiphenyl. The melting point was 125.6 to 126.6C. There were mixed 11.50 g (0.022 mole) of N-(4-tert-butylphenyl)-N,N'-diphenyl-4,4'-diaminobiphenyl, 5.00 g (0.01 mole) of 4,4"-diiodo-p-terphenyl, 4.14 g (0.030 mole) of anhydrous potassium carbonate, 0.32 g (0.005 mole) of copper powder and 10 ml of n-dodecane, followed by reaction at 195 to 210C for 30 hours. The reaction product was extracted with 400 ml of toluene, and the insoluble matter was removed by filtration. Then, the filtrate was concentrated. After the concentration, 60 ml of methanol was added to perform crystallization, and suction filtration was performed to obtain crude crystals. The crude crystals were dissolved in 50 ml of toluene under reflux, and allowed to cool down to 45C. Then, 100 ml of ethyl acetate was added dropwise to perform crystallization, thereby obtaining crystals. N,N'-bis[4-(4-tert-butyldiphenylamino)biphenyl-4'-yl]-N,N'-diphenyl-4,4"-diamino-p-terphenyl was obtained in an amount of 6.70 g. The yield was 57.5%, and the HPLC purity was 95.6%. The crystals were purified by column chromatography (carrier: silica gel, eluate: toluene/n-hexane=1/2) to obtain 4.00 g (HPLC purity: 99.9%, column purification yield: 62.5%) of N,N'-bis[4-(4-tert-butyldiphenylamino)biphenyl-4'-yl]-N,N'-diphenyl-4,4"-diamino-p-terphenyl. The melting point was 209.5C. Identification of the product was performed by NMR analysis, elemental analysis and IR analysis. The elemental analysis values are as follows: carbon; measured value; 88.96% (theoretical value; 88.77%), hydrogen; measured value; 6.65% (theoretical value; 6.41%), nitrogen; measured value; 4.57% (theoretical value; 4.82%). The results of NMR analysis were as follows: 7.629 ppm (4H), 7.545-7.425 (12H), 7.283-7.033 ppm (40H), 1.317 ppm (18H).

Reference： [1]Patent: EP1698613,2006,A1 .Location in patent: Page/Page column 12

26
[ 27973-29-1 ]
[ 4496-49-5 ]
C₄₈H₄₄N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃;	Preparation Example 2 (Synthesis of Compound (2)) Under the stream of argon, 3.6 g (10 mmole) of 1,6-dibromopyrene, 5.6 g (25 mmole) of 4-t-butyldiphenylamine, 0.03 g (1.5% by mole) of palladium acetate, 0.06 g (3% by mole) of tri-t-butylphosphine, 2.4 g (25 mmole) of t-butoxysodium and 100 ml of dry toluene were placed into a 300 ml three-necked flask equipped with a condenser, and the resultant mixture was heated at 100 C under stirring for one night. After the reaction was completed, the formed crystals were separated by filtration and washed with 50 ml of toluene and 100 ml of methanol, and 5.1 g of a light yellow powder substance was obtained. The obtained product was identified to be Compound (2) from the 1H-NMR spectrum (Figure 2) and by the measurement in accordance with FD-MS (the yield: 79%). The 1H-NMR spectrum was obtained under the same condition as that in Synthesis Example 1.

Reference： [1]Patent: EP1790631,2007,A1 .Location in patent: Page/Page column 11

27
[ 1005197-05-6 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium t-butanolate; DavePhos;palladium dibenzylideneacetone; In toluene; at 80℃; for 16h;	Example 7 Preparation of N-(4-tert-butylphenyl)aniline In a drybox, a glass thick-walled pressure tube is charged with 0.055 mL (0.6 mmoL) of aniline, 0.157 g (0.5 mmol) of 4-tert-butylphenyl 2-hydrotetrafluoroethane sulfonate, 0.067 g (0.7 mmol) of sodium t-butoxide, 0.02 g (0.05 mmol) of 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 0.023 g (0.025 mmol) of palladium dibenzylideneacetone and 2 mL of toluene. The tube is sealed, brought out of the drybox and heated at 80 C. for 16 h. The reaction mixture is cooled to room temperature, the tube is opened, and ether is added and the mixture is passed through a small plug of celite. The solvents are removed in vacuo. The crude product is purified on a 20 g silica gel column using 5% ethyl acetate/hexane. Removal of volatiles yields 0.096 g (86%) of N-(4-tert-butylphenyl)aniline as a light brown oil. The proton NMR is identical to that of N-(4-tert-butylphenyl)aniline as given in the literature. This reaction goes in good yield is in contrast to the reaction of 4-tert-butylphenyl 1-hydrotetrafluoroethane sulfonate with aniline, which gives a complex mixture of products.
86%	With sodium t-butanolate; DavePhos;palladium dibenzylideneacetone; In toluene; at 80℃; for 16h;	Example 6Preparation of N-(4-tert-butylphenyl)anilineIn a drybox, a glass thick-walled pressure tube is charged with 0.055 mL (0.6 mmoL) of aniline, 0.157 g (0.5 mmol) of 4-tert-butylphenyl 2-hydrotetrafluoroethane sulfonate, 0.067 g (0.7 mmol) of sodium t-butoxide, 0.02 g (0.05 mmol) of 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 0.023 g (0.025 mmol) of palladium dibenzylideneacetone and 2 mL of toluene. The tube is sealed, brought out of the drybox and heated at 80 C. for 16 h. The reaction mixture is cooled to room temperature, the tube is opened, and ether is added and the mixture is passed through a small plug of celite. The solvents are removed in vacuo. The crude product is purified on a 20 g silica gel column using 5% ethyl acetate/hexane. Removal of volatiles yields 0.096 g (86%) of N-(4-tert-butylphenyl)aniline as a light brown oil. The proton NMR is identical to that of N-(4-tert-butylphenyl)aniline as given in the literature. This reaction goes in good yield is in contrast to the reaction of 4-tert-butylphenyl 1-hydrotetrafluoroethane sulfonate with aniline, which gives a complex mixture of products.

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 711 - 714
[2]Patent: US2009/137831,2009,A1 .Location in patent: Page/Page column 6
[3]Patent: US2009/137840,2009,A1 .Location in patent: Page/Page column 5

28
[ 821808-30-4 ]
[ 4496-49-5 ]
C₆₇H₅₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		(Synthesis of Exemplified Compound No. 4); Under a nitrogen atmosphere, 458 mg (0.797 mmol) of bis (benzylidene acetone) palladium and 0.97 g (4.78 mmol) of tri-tert-butylphosphine were dissolved in 200 ml of xylene, and the whole was stirred for 1 hour at room temperature. After 100 ml of xylene had been further added to the solution, 3 g (4.98 mmol) of Intermediate (II) was added to the mixture in a stream of nitrogen, and the whole was stirred for 5 minutes in an oil bath heated to 50C. 2.24 g (9.96 mmol) of N- (4-T-BUTYLPHENYL)-N-PHENYLAMINE was dissolved in 50 ml of xylene, and the resultant solution was added dropwise into the mixture. Subsequently, 1.43 g (14.9 mmol) of sodium tert- butoxide was added to the mixture. The mixture was heated and stirred for about 5 hours in an oil bath heated to 130C. After the temperature of the reaction solution had been returned to room temperature, 100 ml of water was added to the reaction solution, and a water layer was separated from an organic layer. Furthermore, the water layer was extracted with toluene and ethyl acetate, and dried along with the organic layer by using sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (toluene : hexane = 1 : 3), resulting in 2.9 g of Exemplified Compound No. 5.

Reference： [1]Patent: WO2005/787,2005,A1 .Location in patent: Page 47-49

29
[ 59970-38-6 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With water; potassium carbonate;palladium diacetate; dicyclohexyl-(2?,4?,6?-triisopropyl-3,6-dimethoxy-[1,1?-biphenyl]-2-yl)phosphine; In tert-butyl alcohol; at 110℃; for 4h;Inert atmosphere;Product distribution / selectivity;	EXAMPLE THIRTEEN: Experimental Procedures for Reactions Described in Table 4, Figure 8; General Procedure Using the Precatalysts An oven-dried test tube, which was equipped with a magnetic stir bar and fitted with a teflon septum, was charged with the precatalyst (1 mol%), ligand (1 mol%), 4-t- butylphenyl methanesulfonate (0.5 mmol, 114 mg), and K2CO3 (97 mg, 0.7 mmol). The vessel was evacuated and backfilled with argon (this process was repeated a total of 3 times) and then the aniline (55 muL, 0.6 mmol) and tert-butanol (6 mL) were added via syringe. The solution was heated to 110 0C for 4 h, cooled to room temperature, diluted with Ethyl acetate, and washed with water. Dodecane was then added as an internal standard and the reaction was analyzed by GC.General Procedure for Water-Mediated Catalyst PreactivationAn oven-dried test tube, which was equipped with a magnetic stir bar and fitted with a teflon septum, was charged with Pd(OAc)2 (1 mol%) and ligand (3 mol%). The vessel was evacuated and backfilled with argon (this process was repeated a total of 3 times) and the tert-butanol (1 mL) and degassed H2O (8 mol%) were added via syringe. After addition of the water, the solution was heated to 110 0C for 1 min.A second oven-dried test tube, which was equipped with a magnetic stir bar and fitted with a Teflon septum, was charged with 4-t-butylphenyl methanesulfonate (0.5 mmol, 114 mg) and K2CO3 (97 mg, 0.7 mmol). The vessel was evacuated and backfilled with argon (this process was repeated a total of 3 times) and then the aniline (55 muL, 0.6 mmol) and tert-butanol (5 mL) were added via syringe and the activated catalyst solution was transferred from the first reaction vessel into the second via cannula. The solution was heated to 110 0C for 4 h, cooled to room temperature, diluted with Ethyl acetate, and <n="125"/>washed with water. Dodecane was then added as an internal standard and the reaction was analyzed by GC.

Reference： [1]Patent: WO2009/76622,2009,A2 .Location in patent: Page/Page column 123-124
[2]Journal of the American Chemical Society,2008,vol. 130,p. 13552 - 13554

30
[ 4496-49-5 ]
[ 22401-74-7 ]

Reference： [1]Journal of Organic Chemistry,2009,vol. 74,p. 4720 - 4726

31
[ 62-53-3 ]
[ 154318-75-9 ]
[ 4496-49-5 ]

Reference： [1]Journal of Organic Chemistry,2009,vol. 74,p. 4720 - 4726

32
[ 769-92-6 ]
[ 1078-58-6 ]
[ 4496-49-5 ]

Reference： [1]Organic Letters,2011,vol. 13,p. 5998 - 6001

33
[ 80516-57-0 ]
[ 4496-49-5 ]

Reference： [1]Organic Letters,2012,vol. 14,p. 5488 - 5491,4

34
[ 108-86-1 ]
[ 769-92-6 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
	With C22H26Cl2NPPd; sodium t-butanolate; In toluene; at 110℃; for 22h;Inert atmosphere;	General procedure: Under a nitrogen atmosphere, an 8-mL vial was charged with NaOtBu (135 mg, 1.40 mmol), toluene (2 mL), aryl halide (1.0 mmol), amine (1.2 mmol) and (3IP)PdCl2 (5.6 mg, 11 mumol, 1.1 mol%). For the lower boiling amines (as noted in the data tables), 8 mL of toluene was used in order to minimize headspace within the vial. The reaction mixture was stirred and heated at 110 C for 22 h. An aliquot of the resulting mixture was diluted with diethyl ether (1.8 mL), filtered through an alumina column and analyzed by gas chromatography. Bulk products were then isolated via column chromatography (silica; 10% ethyl acetate in pentane, unless otherwise noted) and further characterized by 1H and 13C NMR spectroscopy, as well as high-resolution mass spectrometry.

Reference： [1]Journal of Organometallic Chemistry,2012,vol. 720,p. 7 - 18,12

35
[ 769-92-6 ]
[ 108-90-7 ]
[ 1410783-24-2 ]
[ 4496-49-5 ]

Reference： [1]Organic Letters,2012,vol. 14,p. 5964 - 5967

36
[ 122-39-4 ]
[ 115-11-7 ]
[ 4627-22-9 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
	With H-BEA zeolite CP 814E; In n-heptane; at 180℃; for 2h;Inert atmosphere;Catalytic behavior;	The alkylation of diphenylamine was carried out in the laboratory autoclave reactor (100 ml) equipped with magnetic stirring and electrical heating with temperature regulation. The weighted amount of liquid isobutylene or C4-fraction was introduced to the reactor from the special steel sampler through two needle valves after heating the sampler to circa 90 C. In a typical run, diphenylamine (20 mmol), 70 ml n-heptane as a solvent and 0.7 g of freshly calcined zeolite catalyst kept at 200 C after calcination were used in alkylation reactions. The clay catalysts (Nobelin and Fulcat 22B), were used as received without activation procedure because higher temperature has negative influence on the clay structure and its catalytic activity decreases. For reusabitity test, used zeolite catalyst was filtered from reaction mixture, washed with n-heptane and methanol and calcined to remove any trapped organics. Clay catalyst was washed with n-heptane and methanol and dried at 120 C. As to alkylating agents, tert-butanol, isobutylene or isobutylene containing C4-fraction were introduced into autoclave reactor in amount of 40 mmol. The amount of isobutylene containing C4-fraction was calculated to meet IB content of 40 mmol. The reactor was flashed thrice with nitrogen to replace air before adding the alkylating agent. Alkylation reactions were carried out at 180 C and at the autogenous pressure at stirring 1000 min- 1 (see Ref. [22]). The samples of the reaction mixture were withdrawn periodically from the closed reactor and were analyzed on CHROMPACK 9002 gas chromatograph equipped with CP Sil 5 CB column (25 m × 0.53 mm) and FID detector. The temperature program of the chromatographic analysis was: 110 C (5 min), from 110 C to 275 C with a slope of 3 C/min. The reaction products were identified on GC/MS QP5000 (Shimadzu) with EI and capillary column (HP-1, 50 m × 0.2 mm × 0.33 mum), carrier gas was helium (0.5 ml/min). Temperature program: from 110 C with gradient 3 C/min to 270 C. Reaction time 0 min is defined as the time when reaction temperature is reached (180 C). Calculations are based on following formulas: 4,4?-DTBDPA/4-TBDPA = moles of 4,4?-di-tert-butyldiphenylamine/moles of 4-tert-butyldiphenylamine, S4-TBDPA = (4-TBDPA/Sigma TBDPA) × 100, S4,4?-DTBDPA = (4,4?-DTBDPA/Sigma DTBDPA) × 100.

Reference： [1]Catalysis Communications,2012,vol. 18,p. 176 - 181

37
[ 122-39-4 ]
[ 75-65-0 ]
[ 4627-22-9 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
	With H-BEA zeolite CP 814E; In n-heptane; at 180℃; for 2h;Inert atmosphere;Catalytic behavior;	The alkylation of diphenylamine was carried out in the laboratory autoclave reactor (100 ml) equipped with magnetic stirring and electrical heating with temperature regulation. The weighted amount of liquid isobutylene or C4-fraction was introduced to the reactor from the special steel sampler through two needle valves after heating the sampler to circa 90 C. In a typical run, diphenylamine (20 mmol), 70 ml n-heptane as a solvent and 0.7 g of freshly calcined zeolite catalyst kept at 200 C after calcination were used in alkylation reactions. The clay catalysts (Nobelin and Fulcat 22B), were used as received without activation procedure because higher temperature has negative influence on the clay structure and its catalytic activity decreases. For reusabitity test, used zeolite catalyst was filtered from reaction mixture, washed with n-heptane and methanol and calcined to remove any trapped organics. Clay catalyst was washed with n-heptane and methanol and dried at 120 C. As to alkylating agents, tert-butanol, isobutylene or isobutylene containing C4-fraction were introduced into autoclave reactor in amount of 40 mmol. The amount of isobutylene containing C4-fraction was calculated to meet IB content of 40 mmol. The reactor was flashed thrice with nitrogen to replace air before adding the alkylating agent. Alkylation reactions were carried out at 180 C and at the autogenous pressure at stirring 1000 min- 1 (see Ref. [22]). The samples of the reaction mixture were withdrawn periodically from the closed reactor and were analyzed on CHROMPACK 9002 gas chromatograph equipped with CP Sil 5 CB column (25 m × 0.53 mm) and FID detector. The temperature program of the chromatographic analysis was: 110 C (5 min), from 110 C to 275 C with a slope of 3 C/min. The reaction products were identified on GC/MS QP5000 (Shimadzu) with EI and capillary column (HP-1, 50 m × 0.2 mm × 0.33 mum), carrier gas was helium (0.5 ml/min). Temperature program: from 110 C with gradient 3 C/min to 270 C. Reaction time 0 min is defined as the time when reaction temperature is reached (180 C). Calculations are based on following formulas: 4,4?-DTBDPA/4-TBDPA = moles of 4,4?-di-tert-butyldiphenylamine/moles of 4-tert-butyldiphenylamine, S4-TBDPA = (4-TBDPA/Sigma TBDPA) × 100, S4,4?-DTBDPA = (4,4?-DTBDPA/Sigma DTBDPA) × 100.

Reference： [1]Catalysis Communications,2012,vol. 18,p. 176 - 181

38
[ 123324-71-0 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
76%	With C21H16CuN2O2; potassium carbonate; In water; at 28℃; for 18h;	General procedure: A 50 mL round bottomed flask was charged with amine (0.5 mmol), arylboronicacid (0.75 mmol), K2CO3 (1.5 mmol, 207 mg), C-1 complex (20 mol %, 39.15 mg) in 3 mL of water at room temperature. The reaction mixture was stirred with a magnetic stirrer for appropriate time. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was diluted with 20 mL of water and extracted with diethylether (3*20 mL). The combined organic layer were washed with brine and dried over by anhydrous Na2SO4 and evaporated in a rotary evaporator under reduced pressure. The crude was purified by column chromatography on silica gel (hexane/ethyl acetate, 9:1) to afford the desired product.

Reference： [1]Green Chemistry,2018,vol. 20,p. 4891 - 4900
[2]Heteroatom Chemistry,2018,vol. 29
[3]Tetrahedron Letters,2014,vol. 55,p. 31 - 35

39
[ 128-63-2 ]
[ 4496-49-5 ]
N,N',N'',N'''-tetrakis(4-tert-butylphenyl)-N,N',N'',N'''-tetraphenylpyrene-1,3,6,8-tetraamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Schlenk technique; Reflux;	General procedure: To a flask containing a mixture of 1,3,6,8-tetrabromopyrene (0.52 g, 1.0 mmol), diphenylamine (0.74 g, 4.4 mmol), sodium tert-butoxide (0.51 g, 5.28 mmol) and Pd(dba)2 (0.040 mmol) was added dry toluene (30 mL). After 30 min. P(tBu)3 (1.2 mol%) was added and the solution mixture was heated to reflux and stirred for 24 h. After cooling, the solution was pumped dry and the residue was extracted with CH2Cl2/brine. The organic layer was dried over magnesium sulfate, then filtered and dried. After recrystallization from dichloromethane and hexane, the crude product was further purified by column chromatography using CH2Cl2/hexane (1:10 by v/v) as eluent to give 1 as a yellow powder (0.82 g, 92%).

Reference： [1]Organic electronics,2014,vol. 15,p. 2148 - 2157

40
C₁₆H₁₈NO^(1-)*Cl^(1-)*Zn⁽²⁺⁾ [ No CAS ]
[ 4496-49-5 ]

Reference： [1]Chemical Communications,2015,vol. 51,p. 3239 - 3242

41
[ 4496-49-5 ]
C₂₆H₁₄Br₂N₂S₂ [ No CAS ]
C₅₈H₅₀N₄S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium tert-butylate; In toluene; at 85℃; for 12h;	Intermediate Compound 5-4 1.15 g (2.0 mmol), the compound 5-A 0.90 g (4.0 mmol), Pd2 (dba) 3 37 mg (0.04 mmol), PtBu3 8 mg (0.04 mmol) and 0.58 g KOtBu (6.0 mmol) It was dissolved in 30 ml toluene at 85C was stirred for 12 hours. After cooling the reaction solution to room temperature and extracted three times with 30 mL water and 30 mL of diethyl ether. The combined organic layers were dried over magnesium sulfate and purified by separating the residue obtained by evaporation of the solvent by silica jelgwan chromatography to obtain the compound 5 1.44 g (83% yield). The resulting compound was confirmed by LC-MS C58H50N4S2: M +866.36

Reference： [1]Patent: KR2015/66153,2015,A .Location in patent: Paragraph 0284; 0285; 0294; 0295

42
[ 4496-49-5 ]
5',9'-dibromospiro(fluoren-9,7'-fluoreno[4,3-b]benzofuran) [ No CAS ]
(4-tert-butylphenyl)phenylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	In a 250-ml round-bottom flask reactor, a mixture of <Intermediate 1-f>(5.0 g, 0.009 mol), <strong>[4496-49-5](4-tert-butylphenyl)-phenylamine</strong> (4.7 g, 0.021 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) were stirred together for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield the compound of Chemical Formula 1 as a solid (2.9 g, 38%). (0118) MS (MALDI-TOF): m/z 852.41 [M+]
38%	With palladium diacetate; triphenylphosphine; sodium t-butanolate; In toluene; for 2h;Reflux;	In a 250-ml round-bottom flask reactor, a mixture of <Intermediate 10-f> (5.0 g, 0.009 mol), <strong>[4496-49-5](4-tert-butylphenyl)-phenylamine</strong> (4.7 g, 0.021 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) was stirred for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield <BD 2> as a solid (2.9 g, 38%). (0246) MS (MALDI-TOF): m/z 852.41 [M+]
38%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	In a 250-ml round-bottom flask reactor, a mixture of (5.0 g, 0.009 mol), <strong>[4496-49-5](4-tert-butylphenyl)-phenylamine</strong> (4.7 g, 0.021 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) were stirred together for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield the compound of Chemical Formula 1 as a solid (2.9 g, 38%). MS (MALDI-TOF): m/z 852.41 [M+]

38%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	In a 250-ml round-bottom flask reactor, a mixture of (5.0 g, 0.009 mol), (4-tert-butylphe- nyl)-phenylamine (4.7 g, 0.02 1 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) were stirred together for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield the compound of Chemical Formula 1 as a solid (2.9 g, 38%).10138] MS (MALDI-TOF): mlz 852.41 [M+]
38%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	(0172) In a 250-ml round-bottom flask reactor, a mixture of <Intermediate 1-f>(5.0 g, 0.009 mol), (4-tert-butylphenyl)amine (4.7 g, 0.021 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) was stirred for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield the compound of Chemical Formula 1 (2.9 g, 38%). (0173) MS (MALDI-TOF): m/z 852.41 [M+]

Reference： [1]Patent: US2017/12214,2017,A1 .Location in patent: Paragraph 0116-0118
[2]Patent: US2017/18723,2017,A1 .Location in patent: Paragraph 0244-0246
[3]Patent: US2017/141321,2017,A1 .Location in patent: Paragraph 0138-0140
[4]Patent: US2017/133600,2017,A1 .Location in patent: Paragraph 0136; 0137; 0138
[5]Patent: US2018/233669,2018,A1 .Location in patent: Paragraph 0171-0172

43
[ 201230-82-2 ]
[ 4496-49-5 ]
2-(tert-butyl)acridin-9(10H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With di-tert-butyl peroxide; palladium dichloride; In dimethyl sulfoxide; at 100℃; for 24h;Schlenk technique;	Was added in a dry Schlenk reaction tubePalladium chloride (0.025 mmol), copper pivalate (0.05 mmol),P-tert-butyldiphenylamine (0.25 mmol), the system was replaced three times under one atmosphere of carbon monoxide atmosphere. Then, the solvent was added successively to dry dimethylsulfoxide (1.0 mL)DTBP (0.75 mmol) and solvent dry dimethylsulfoxide (2.0 mL)The reaction was stopped at 100 C for 24 hours,After cooling to room temperature, ethyl acetate was added to the reaction system to quench the reaction, a saturated potassium carbonate solution (30.0 mL) was added, and the mixture was extracted with dichloromethane (20 × 3). The acridone derivative was isolated by column chromatography,Separation yield of 75%

Reference： [1]Patent: CN106187890,2016,A .Location in patent: Paragraph 0034; 0035; 0036; 0037
[2]Organic Letters,2017,vol. 19,p. 94 - 97

44
[ 5400-88-4 ]
[ 108-94-1 ]
[ 4496-49-5 ]

Reference： [1]Chemical Science,2017,vol. 8,p. 2131 - 2142

45
[ 769-92-6 ]
[ 108-94-1 ]
[ 4496-49-5 ]

Reference： [1]Chemical Science,2017,vol. 8,p. 2131 - 2142
[2]Chemical Communications,2017,vol. 53,p. 10827 - 10830

46
[ 98-53-3 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Reference： [1]Advanced Synthesis and Catalysis,2018,vol. 360,p. 3297 - 3305
[2]Chemical Science,2017,vol. 8,p. 2131 - 2142

47
[ 108-91-8 ]
[ 98-53-3 ]
[ 4496-49-5 ]

Reference： [1]Chemical Science,2017,vol. 8,p. 2131 - 2142

48
[ 4496-49-5 ]
C₃₁H₁₇BrO [ No CAS ]
C₄₇H₃₅NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	Synthesis Example 1-(7): Synthesis of Compound of Chemical Formula 2 (0111) (0112) In a 250-ml round-bottom flask reactor, a mixture of [Intermediate 1-f] (4.4 g, 0.009 mol), <strong>[4496-49-5](4-tert-butylphenyl)-phenylamine</strong> (4.7 g, 0.021 mol), palladium (II) acetate (0.08 g, 0.4 mmol), sodium tert-butoxide (3.4 g, 0.035 mol), tri-tert-butyl phosphine (0.07 g, 0.4 mmol), and toluene (60 ml) were stirred together for 2 hrs under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and then extracted with dichloromethane and water. The organic layer thus formed was separated, dried over magnesium sulfate, and concentrated in a vacuum. The concentrate was purified by column chromatography and recrystallized in dichloromethane and acetone to yield the compound of Chemical Formula 2 as a solid (3.3 g, 58%) (0113) MS (MALDI-TOF): m/z 629.27 [M+]

Reference： [1]Patent: US2017/141322,2017,A1 .Location in patent: Paragraph 0111; 0112; 0113

49
[ 4496-49-5 ]
C₃₅H₂₀BrF [ No CAS ]
4-(tert-butyl)-N-(4-(13-(4-fluorophenyl)-13H-benzo[5,6]indeno[1,2-a]acenaphthylen-13-yl)phenyl)-N-phenylaniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66.19%	With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 105 - 108℃; for 7h;Inert atmosphere;	The compound VIII (10.8 g, 20.0 mmol) obtained in step (3), 4-tert-butyl-N-phenylaniline (5.0 g, 22 mmol), sodium tert-butoxide (2.9 g, 30 mmol) and 200 g of toluene, under nitrogen protection, was added palladium acetate (135 mg, 0.6 mmol) and P(T-Bu)3·HBF4 (348 mg, 1.2 mmol) and reacted at 105 to 108 C for 7.0 hours while TLC followed the reaction. After completion of the reaction, adding 300 g of water to quench the reaction, the system layer, the use of washed organic phase, the organic phase decompression solvent to no fractions. The residue was then subjected to column chromatography with a mixture of petroleum ether and ethyl acetate. The volume ratio of petroleum ether to ethyl acetate was petroleum ether: ethyl acetate = 4: 1, 11.0 g of compound 15 was obtained, and further the crude product was sublimed in a chemical vapor deposition system at 320 C to give 9.2 g of a white solid powder in a yield of 66.19%.

Reference： [1]Patent: CN106883145,2017,A .Location in patent: Paragraph 0083; 0084; 0085

50
[ 769-92-6 ]
[ 98-80-6 ]
[ 4496-49-5 ]
[ 7775-81-7 ]

Reference： [1]Dalton Transactions,2017,vol. 46,p. 12766 - 12770
[2]ACS Catalysis,2018,vol. 8,p. 7308 - 7325

51
[ 98-53-3 ]
[ 98-95-3 ]
[ 4496-49-5 ]

Reference： [1]Catalysis science and technology,2017,vol. 7,p. 2170 - 2182

52
[ 4496-49-5 ]
C₃₁H₂₂BrN [ No CAS ]
C₄₇H₄₀N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66.82%	With palladium diacetate; sodium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In 5,5-dimethyl-1,3-cyclohexadiene; at 120 - 130℃; for 12h;Inert atmosphere;	In a 250 ml three-necked flask, Intermediate 1-IV (4.88 g, 0.01 mol), N-phenyl- (4-t- butyl) aniline (2.48 g, 0.011 mol) Sodium carbonate (1.92 g, 0.02 mol), palladium acetate (22 mg, 0.1 mmol), P (t-Bu) 3HBF4 (58 mg, 0.2 mmol) and 60 mL of xylene were added and reacted at 120-130 C. for 12 h. , The organic phase was depressurized to remove the solvent, purified by column chromatography, and recrystallized from toluene and petroleum ether to give the target product C07 in a yield of 66.82%.

Reference： [1]Patent: CN107353249,2017,A .Location in patent: Paragraph 0097; 0098; 0099; 0100

53
[ 4496-49-5 ]
C₃₇H₁₉Cl₂N [ No CAS ]
C₆₉H₅₅N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 5h;Reflux;	Compound a 10.0 g (1.0 eq),10.40 g (2.2 eq) of 4- (tert-butyl) -N-phenylaniline, 0.05 g (0.005 eq) of Pd (t-Bu3P) 2 and 5.25 g (3.0 eq) of NaOtBu were placed in 100 mL of xylene and refluxed and stirred.After 5 hours, the reaction mixture was cooled to room temperature, and then the xylene was removed by decompression. The reaction solution was completely dissolved in CHCl 3 and washed with water. The solvent was removed under reduced pressure to purify the residue by column chromatography,9.40 g (yield 70%) of Compound 8 was obtained.

Reference： [1]Patent: KR2018/323,2018,A .Location in patent: Paragraph 0432-0435

54
[ 4496-49-5 ]
C₃₇H₁₉Cl₂N [ No CAS ]
C₆₉H₅₅N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 5h;Reflux;	Compound d 10.0 g (1.0 eq),To 100 mL of Xylene was added 9.03 g (2.2 eq) of 4- (tert-butyl) -N-phenylaniline, 0.05 g (0.005 eq) of Pd (t-Bu3P) 2 and 5.25 g (3.0 eq) of NaOtBu, .After 5 hours, the reaction mixture was cooled to room temperature, and then the xylene was removed by decompression. The reaction solution was completely dissolved in CHCl 3 and washed with water. The solvent was then removed under reduced pressure and purified by column chromatography.11.82 g (yield 70%) of Compound 8 was obtained.

Reference： [1]Patent: KR2018/322,2018,A .Location in patent: Paragraph 0447; 0450

55
[ 4496-49-5 ]
C₄₅H₂₃Br₂NO [ No CAS ]
C₇₇H₅₉N₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 3h;Inert atmosphere; Reflux;	To a 500 ml round-bottomed flask in a nitrogen atmosphere was added Compound A (5.48 g, 7.30 mmol)4- (tert-butyl) -N-phenylaniline (3.28 g, 14.59 mmol)Was completely dissolved in 240 ml of xylene, sodium terbutoxide (1.82 g, 18.97 mmol) was added, Bis (tri-tert-butylphosphine) palladium (0) (0.07 g, 0.15 mmol) was added and the mixture was heated and stirred for 3 hours.After the temperature was lowered to room temperature, the base was removed by filtration, the xylene was concentrated under reduced pressure and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1:30. The solvent was completely concentrated under reduced pressure and recrystallized from ethyl acetate (110 ml) to give Compound 8 (3.22 g, purity: 100%, yield: 42%).

Reference： [1]Patent: KR2018/32500,2018,A .Location in patent: Paragraph 0209-0213

56
[ 4496-49-5 ]
C₄₅H₂₃Br₂NS [ No CAS ]
C₇₇H₅₉N₃S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 4h;Inert atmosphere; Reflux;	To a 500 ml round-bottomed flask under nitrogen was added compound B (4.71, 6.14 mmol),(2.76 g, 12.28 mmol) of 4- (tert-butyl) -N-phenylaniline was completely dissolved in 210 ml of xylene, sodium terbutoxide (1.53 g, 15.97 mmol)Bis (tri-tert-butylphosphine) palladium (0) (0.06 g, 0.12 mmol) was added and the mixture was heated with stirring for 4 hours.After lowering the temperature to room temperature, removing the base by filtration, concentrate the xylene under reduced pressure, and column with tetrahydrofuran: hexane = 1:25. The solvent was completely concentrated under reduced pressure and recrystallized from 120 ml of ethyl acetate to give the above compound 10 (3.87 g, purity: 100%, yield: 60%).

Reference： [1]Patent: KR2018/32500,2018,A .Location in patent: Paragraph 0221-0225

57
[ 4496-49-5 ]
5',9'-dibromospiro(fluoren-9,7'-fluoreno[4,3-b]benzofuran) [ No CAS ]
C₄₇H₃₄BrNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 2h;Reflux;	In a 250 ml round bottom flask <Intermediate 1-f> (5.0 g, 0.009 mol), (4-tert-butylphenyl) -phenylamine (2.5 g, 0.011 mol), Palladium (II) acetate (0.08 g, 0.4 mmol),Sodium tertiary butoxide (3.4 g, 0.035 mol), Tree-tert-butylphosphine (0.07 g, 0.4 mmol),60 ml of toluene was added and the mixture was refluxed and stirred for 2 hours.After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography, and then recrystallized from dichloromethane and acetone to obtain Intermediate 1-g. (2.2 g, 35%).

Reference： [1]Patent: KR2018/60619,2018,A .Location in patent: Paragraph 0425; 0450-0453

58
[ 4496-49-5 ]
C₃₉H₂₀Br₂O₂ [ No CAS ]
C₇₁H₅₆N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene;Reflux;	P-1-1 (10 g, 14.7 mmol) and4- (tert-butyl) -N-phenylaniline (6.69 g, 29.7 mmol),Sodium-t-butoxide (3.53 g, 36.7 mmol) was added to xyleneAnd the mixture was heated and stirred, then refluxed and [bis (tri-t-butylphosphine)] palladium (150 mg, 2 mol%) was added.After the temperature was lowered to room temperature and the reaction was terminated,Tetrahydrofuran and ethyl acetate were addedTo prepare Compound 1. (9.97 g, 70% yield)

Reference： [1]Patent: KR2018/75914,2018,A .Location in patent: Paragraph 0400-0403

59
[ 4496-49-5 ]
N-(4-bromophenyl)-N-phenylbenzo[b]thiophen-3-amine [ No CAS ]
C₃₆H₃₂N₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	To a round bottom flask was added N- (4-bromophenyl) -N-phenylbenzo [b] thiophen-3-amine(9.1 g, 24 mmol) was added to a solution of 4-tert-butyl-N-phenylaniline (4.5 g, 20 mmol)Pd2 (dba) 3 (0.03-0.05 mmol), P (t-Bu) 3 (0.1 eq), NaOt-Bu (3 eq)toluene (10.5 mL / 1 mmol) is added and the reaction proceeds at 100 C.After completion of the reaction, the reaction mixture was extracted with ether and water, and the organic layer was dried over MgSO4The concentrate was purified by silica gel column and recrystallized to obtain 7.0 g (yield: 67%) of the product.

Reference： [1]Patent: KR101896063,2018,B1 .Location in patent: Paragraph 0047; 0079-0081

60
[ 1943-67-5 ]
[ 88284-48-4 ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
51%	With cesium fluoride; In acetonitrile; at 100℃; for 14h;Inert atmosphere;	General procedure: A mixture of benzyne precursor (0.1 mmol) and p-toluenesulfonyl isocyanate (0.24 equiv.) and cesium fluoride (0.3 equiv.) in acetonitrile (0.1 M) was heated at 100C for 14h. The reaction was quenched with H2O and extracted with ethyl acetate (3 x 2 ml). The combined organic extract was dried over anhydrous sodium sulfate (Na2SO4), filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give the desired product.

Reference： [1]Tetrahedron Letters,2018,p. 671 - 674

61
[ 92-86-4 ]
[ 4496-49-5 ]
N₄,N₄'-bis(4-(tert-butyl)phenyl)-N₄,N₄'-diphenyl-[1,1'-biphenyl]-4,4'-diamine [ No CAS ]

Reference： [1]Journal of Materials Chemistry C,2018,vol. 6,p. 12355 - 12363

62
[ 4496-49-5 ]
C₃₁H₂₆BrNS₂Si [ No CAS ]
C₄₇H₄₄N₂S₂Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	To a round bottom flask was added 4-tert-butyl-N-phenylaniline (4.5 g, 20 mmol), Dithienosilole compound (14.0 g, 24 mmol),Pd2 (dba) 3 (0.05 eq), P (t-Bu) 3 (0.1 eq) NaOt-Bu (3 eq.) And toluene (10.5 mL / 1 mmol) are added, and the reaction proceeds at 100 C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.32 g of product. (Yield: 64%)

Reference： [1]Patent: KR101907671,2018,B1 .Location in patent: Paragraph 0117-0119

63
[ 4496-49-5 ]
2-(5-bromopyridin-2-yl)-6,6-dimethyl-6H-isoindolo[2,1-a]indole [ No CAS ]
C₃₈H₃₅N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	A solution of 2- (5-bromopyridin-2-yl) -6,6-dimethyl-6H-isoindolo [2,1-a] indole (9.34 g, 24 mmol)4-tert-butyl-N-phenylaniline (4.51 g, 20 mmol),Pd2(dba)3 (0.03-0.05 mmol), P(t-Bu)3 (0.1 equivalent)NaOt-Bu (3 eq.) And toluene (10.5 mL / 1 mmol) were added thereto, followed by reaction at 100 C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.62 g (yield: 62%) of the product.

Reference： [1]Patent: KR101971877,2019,B1 .Location in patent: Paragraph 0120-0122

64
[ 78-33-1 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Reference： [1]Journal of Organic Chemistry,2019

65
[ 78-32-0 ]
[ 62-53-3 ]
[ 4496-49-5 ]

Reference： [1]Journal of Organic Chemistry,2019,vol. 84,p. 6366 - 6376

66
[ 4496-49-5 ]
4-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-4H-benzo[b][1,4]thiazine [ No CAS ]
C₃₉H₃₆N₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	4- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -4H-benzo [b] [1,4] thiazine (10.1 g, 24 mmol) in a round bottom flask,4-tert-butyl-N-phenylaniline (4.5 g, 20 mmol), Pd2 (dba) 3 (0.05 equiv), P (t-Bu) 3 (0.1 equiv), NaOt-Bu (3 equiv), toluene (10.5 mL / 1 mmol) and then proceed with the reaction at 100 C. After completion of the reaction, the mixture was extracted with ether and water, and the organic layer was dried over MgSO 4, concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 7.6 g of the product. (Yield 67%)

Reference： [1]Patent: KR102004447,2019,B1 .Location in patent: Paragraph 0095-0097

67
[ 4496-49-5 ]
[ 93-91-4 ]
(1-(4-(tert-butyl)phenyl)-5-((4-(tert-butyl)phenyl)(phenyl)amino)-2-methyl-1H-indol-3-yl)(phenyl)methanone [ No CAS ]

Reference： [1]Organic Letters,2019,vol. 21,p. 6736 - 6740

68
[ 4496-49-5 ]
C₁₈H₁₀Cl₂ [ No CAS ]
C₅₀H₄₆N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 5h;Reflux;	The core 7 (10 g, 33.6 mmol) and the amine compound (15.1 g, 67.2 mmol) were added to xylene (400 mL).NatBuO (16.1 g) and BTP (0.4 g) were added, followed by stirring and reflux for 5 hours.After cooling to room temperature, the solid produced by filtration was recrystallized with ethyl acetate three times to give Compound 13 (11.3 g, yield 50%)

Reference： [1]Patent: KR2019/118515,2019,A .Location in patent: Paragraph 0252-0254

69
[ 4496-49-5 ]
C₄₆H₃₄Cl₂N₂O₆ [ No CAS ]
C₇₈H₇₀N₄O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		11.7 g (15 mmol) of compound 4-F, 37.5 mmol of sodium tert-butoxide, 30 mmol of 4- (tert-butyl) -N-phenylaniline and 100 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenyl 0.2 mmol of phosphine palladium was added and the mixture was stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform to obtain 13.6 g of Compound 10 (yield 78%).

Reference： [1]Patent: KR2019/106774,2019,A .Location in patent: Paragraph 0317; 0322-0325

70
[ 4496-49-5 ]
C₂₈H₁₀F₁₈O₇S₂ [ No CAS ]
C₅₂H₄₆N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
39%	With sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 5h;Reflux;	Compound A-2 (15.0 g, 30.3 mmol) And compound B-2 (13.7 g, 60.6 mmol) Was added to xylene (400 mL). After adding NatBuO (17.5 g) and BTP (0.2 g), Stir and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with three ethyl acetate to obtain Compound 2. (8.4 g, 39% yield).

Reference： [1]Patent: KR2019/118514,2019,A .Location in patent: Paragraph 0270-0273

71
[ 4496-49-5 ]
C₂₈H₁₂Cl₂O₂S [ No CAS ]
C₆₀H₄₈N₂O₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In toluene; at 150℃; for 12h;	[Intermediate 10-6] 6.6 mmol,3.2 g of toluene was dissolved in 60 mL of NatBuO 26.4 mmol,2.5 g was added thereto, stirred at 150 C., and then 6.7 mmol, 1.2 g of 4- (tert-butyl) -N-phenylaniline, 0.058 mmol and 0.03 g of BTP were added sequentially. After 12 h, the reaction was completed, quenched with NH 4 Cl, extracted, and the organic layer was dried over anhydrous MgSO 4, filtered, and concentrated under reduced pressure.The obtained organic material was columned with EA: Hx to obtain compound 10, 3.3 mmol, and 2.8 g (yield 49%).3 shows an LC-Mass measurement graph of Compound 10.

Reference： [1]Patent: KR2019/111687,2019,A .Location in patent: Paragraph 0385; 0410-0413

72
[ 4496-49-5 ]
C₄₀H₂₄Br₂O₂ [ No CAS ]
C₇₂H₆₀N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 5h;Heating;	Compound M (2.5 g, 3.6 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere,4- (tert-butyl)-N-phenylaniline(<strong>[4496-49-5]4-(tert-butyl)-N-phenylaniline</strong>, 1.7 g, 7.56 mmol)After completely dissolved in 160 ml of xylene, sodium tert-butoxide (0.9 g, 9.37 mmol) was added,Bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0), 0.04 g, 0.08 mmol) was added thereto, and the mixture was heated and stirred for 5 hours.After cooling to room temperature and removing the base by filtration, xylene was concentrated under reduced pressure and mixed at a weight ratio of 1:25.By column with tetrahydrofuran and hexane Compound 9 (2.34 g, purity: 99.99%, yield: 66%) was prepared

Reference： [1]Patent: KR2019/138435,2019,A .Location in patent: Paragraph 0284-0287

73
[ 603-76-9 ]
[ 4496-49-5 ]
N,5-bis(4-(tert-butyl)phenyl)-6-methyl-N-phenyl-5,6-dihydroindolo[2,3-b]indol-2-amine [ No CAS ]

Reference： [1]Chemical Communications,2020,vol. 56,p. 2807 - 2810

74
[ 7252-86-0 ]
[ CAS Unavailable ]
[ 4496-49-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; lithium hexamethyldisilazane; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 100℃; for 12h;

Reference： [1]Bismuto, Alessandro; Delcaillau, Tristan; Müller, Patrick; Morandi, Bill [ACS Catalysis, 2020, vol. 10, # 8, p. 4630 - 4639]

75
[ 4496-49-5 ]
[ 2566680-42-8 ]
[ 2566679-96-5 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 110℃; for 3h; Inert atmosphere;	Put the intermediate IM-Q-1 (20g, 38.3mmol) into the reaction flask,SM-L (4496-49-5) (8.6g, 38.3mmol), tris(dibenzylideneacetone)dipalladium (0.35g, 0.38mmol), 2-dicyclohexylphosphine-2,4,6,- Triisopropylbiphenyl (0.35g, 0.76mmol), sodium tert-butoxide (5.5g, 57.3mmol) and toluene solvent (160mL) were heated to 110°C under nitrogen protection, and heated under reflux with stirring for 3h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water. The organic layer was dried over anhydrous magnesium sulfate and filtered. After filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and dichloromethane/n-heptane was used. The system (1:3) was used to recrystallize and purify the crude product to obtain compound 146 (19.1 g, yield: 70%).

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO - CN111995533, 2020, A Location in patent: Paragraph 0237-0238

76
[ 4496-49-5 ]
[ 2581126-74-9 ]
[ 2581125-17-7 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 1h;	Preparation of intermediate 7-iodo-N,N-diphenylpyrido[2,3,4,5-lmn]phenanthridin-2-amine (A-1) General procedure: In the reaction vessel, 3-0 substance (200.2g, 75mmol), sodium tetrabutoxide (21.62g, 225mmol), toluene (500mL),Diamine (12.69g75mmol),Pd2(dba)3 (2.06g, 2.25mmol) and tritetrabutyl phosphine (0.36mL, 15mmol) were added and reacted at 110° C. for 1 hour. The reaction solution was cooled, washed with water, and the palladium catalyst was removed with a silica filter, evaporated to dryness, and recrystallized with methylene chloride/petroleum ether to obtain A-1 (14.92 g, 40%).

Reference： [1]Current Patent Assignee: CHOI, DON SOO - KR102201028, 2021, B1 Location in patent: Paragraph 0294-0296; 0324-0325; 0329

77
[ 4496-49-5 ]
[ 2581126-79-4 ]
[ 2581125-26-8 ]

Yield	Reaction Conditions	Operation in experiment
77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 1h;	Preparation of intermediate 7-iodo-N,N-diphenylpyrido[2,3,4,5-lmn]phenanthridin-2-amine (A-1) General procedure: In the reaction vessel, 3-0 substance (200.2g, 75mmol), sodium tetrabutoxide (21.62g, 225mmol), toluene (500mL),Diamine (12.69g75mmol),Pd2(dba)3 (2.06g, 2.25mmol) and tritetrabutyl phosphine (0.36mL, 15mmol) were added and reacted at 110° C. for 1 hour. The reaction solution was cooled, washed with water, and the palladium catalyst was removed with a silica filter, evaporated to dryness, and recrystallized with methylene chloride/petroleum ether to obtain A-1 (14.92 g, 40%).

Reference： [1]Current Patent Assignee: CHOI, DON SOO - KR102201028, 2021, B1 Location in patent: Paragraph 0294-0296; 0324-0325; 0330

78
[ 4496-49-5 ]
[ 2636060-20-1 ]
[ 2636063-40-4 ]

Yield	Reaction Conditions	Operation in experiment
77%	With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 100 - 105℃; for 16h; Inert atmosphere;	2.1 1) Synthesis of intermediate D1 Dry the experimental device sufficiently, add 19.4g (45mmol) of C1 and 10.1g (45mmol) of 4-tert-butyl-N-phenylaniline to a 500mL four-necked flask under nitrogen, and then add 250mL of dried and degassed toluene As a solvent, add 6.5g (67.5mmol) sodium tert-butoxide, 0.4g (0.45mmol) Pd2(dba)3 catalyst and 0.8g 1,1'-bis(diphenylphosphine)ferrocene (dppf), raise the temperature To 100-105°C, react for 16h. After the reaction is over, cool to room temperature, dilute with toluene, filter with a pad of silica gel, and remove the solvent from the filtrate by vacuum distillation to obtain a crude product, which is then dissolved and decolorized with xylene and recrystallized to obtain 22.8 g of intermediate D1. The yield is 77% and the HPLC purity is 99.3. %.

Reference： [1]Current Patent Assignee: CHANGZHOU TRONLY-ERAY OPTOELECTRONICS MATERIAL CO LTD - CN112538047, 2021, A Location in patent: Paragraph 0078-0084

79
[ 14862-52-3 ]
[ 4496-49-5 ]
[ 2698368-47-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 10h; Inert atmosphere;	3.1 step 1: After adding chemical formula reactant A-72 (100mmol) and reactant B-72 (110mmol) to 500ml toluene in the reaction vessel, add Pd2(dba)3(1.0mmol), P(t-Bu) under nitrogen atmosphere 3 (5.5mmol), t-BuONa (220mmol). After the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 10 h. Use diatomaceous earth to filter while hot to remove salts and catalysts. After the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing. After separation, the organic phase is retained, and the aqueous phase is extracted with ethyl acetate. Next, the combined organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. With the volume ratio of dichloromethane: petroleum ether of 1:(1-9) as the eluent, the remaining material was purified by column chromatography to obtain intermediate C-72 (33.2g, Ms: 414.77, yield: 80%) ).

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN113121361, 2021, A Location in patent: Paragraph 0096-0099

80
[ 4496-49-5 ]
[ 2411942-96-4 ]
[ 2411941-94-9 ]

Yield	Reaction Conditions	Operation in experiment
67%	With sodium t-butanolate; (benzene-1,3,5-triyl)tris[phosphonic acid] In 5,5-dimethyl-1,3-cyclohexadiene for 5h; Reflux;	13 Preparation Example 13: Synthesis of Compound 13 Compound 13-1 (20.5 g, 32.0 mmol) and Compound 13-2 (14.42 g, 64.0 mmol) were added to xylene (400 mL). NatBuO (18.5 g) and BTP (0.2 g) were added thereto, and the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the mixture was filtered and the resulting solid was recrystallized three times from ethyl acetate to give Compound 13 (19.92 g, yield: 67%, MS: [M+H]+=930).

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - US2022/17544, 2022, A1 Location in patent: Paragraph 0136-0137

81
[ 4496-49-5 ]
[ 2763324-34-9 ]
[ 2763324-04-3 ]

Yield	Reaction Conditions	Operation in experiment
31%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide; dicyclohexyl(2’,4’,6’-triisopropyl-[ 1,1’-bi-phenyl]-2-yl)phosphane In toluene at 105 - 115℃; for 3h; Inert atmosphere;	37 Synthesis Example 1: Synthesis of Compound 4 General procedure: Into the three-necked flask equipped with mechanical stirring, thermometer and spherical condenser, nitrogen (0.100L/min) was introduced for replacement for 15min, and intermediate E-1 (5.0g, 10.3mmol), reactant H-1 (1.74g) were added successively. , 10.3mmol), tris(dibenzylideneacetone)dipalladium (0.09g, 0.10mmol), 2-dicyclohexylphosphorus-2',4',6'-triisopropylbiphenyl (0.09g, 0.2 mmol), sodium tert-butoxide (2.96 g, 30.8 mmol) and toluene (40 mL). The stirring was started, the temperature was raised to 105-115° C. for 3 h, and after the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water, and the organic phase was dried over anhydrous magnesium sulfate. After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 4. (2.07 g, 35% yield),

Reference： [1]Current Patent Assignee: SHAANXI LETTER OPTOELECTRONIC MAT; SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN114133351, 2022, A Location in patent: Paragraph 0174-0179; 0184

82
[ 4496-49-5 ]
[ 2765197-42-8 ]
[ 2771098-49-6 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris(2,2′-bipyridyl)ruthenium(II) chloride; Sodium hydrogenocarbonate In acetonitrile at 20℃; for 8h; Inert atmosphere; Irradiation;	4 Example 4 Under light conditions, diphenylamine derivative 1d (1equiv), diazonium trivalent iodine reagent 2a (1.5equiv), ruthenium terpyridine chloride (2% mmol), sodium bicarbonate (1equiv) and acetonitrile (2mL) were added to 15mL In the reaction tube, the mixture was stirred at room temperature for 8 hours, and separated by silica gel column chromatography to obtain the target compound 3d in a yield of 76%.

Reference： [1]Current Patent Assignee: CHANGZHOU UNIVERSITY - CN114436959, 2022, A Location in patent: Paragraph 0025; 0032-0033

83
[ 4496-49-5 ]
[ 2773431-93-7 ]
[ 2773429-23-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene for 3h; Reflux; Inert atmosphere;	1 Synthesis of Compound A1: In a three-necked flask, firstly add M1 (15g, 33.8mmol), A1-1 (7.6g, 33.8mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.3g, 3.38mmol, 1% eq), tri-tert-butylphosphine (t-Bu3P, 1 mL, 1.0 mmol), sodium tert-butoxide (NaOBu-t, 6.4 g, 67.7 mmol), then toluene (100 mL) was added, the system was replaced with nitrogen, and the reaction solution was warmed to Reflux, stirring reaction for 180min. The reaction solution was lowered to 70°C, and the silica gel column was superheated while hot. The mother liquor was concentrated to 70 mL, 30 mL of ethanol was added, stirred at room temperature for 1 h, and filtered. 120 mL of toluene was added to the solid, the mixture was refluxed to dissolve, 100 mL of petroleum ether was added, stirred at room temperature for 2 h, and filtered. Toluene:petroleum ether 2:1 chromatography column separation, the solution was spin-dried to obtain 15g of white solid, the yield was 70%.

Reference： [1]Current Patent Assignee: SHANGHAI KEYI ELECTRONIC TECH - CN114507222, 2022, A Location in patent: Paragraph 0114-0115; 0124-0125

84
[ 4496-49-5 ]
[ 1639407-51-4 ]
[ 2222057-46-5 ]

Yield	Reaction Conditions	Operation in experiment
67%	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene for 12h; Inert atmosphere; Reflux;	1-4 Synthesis Example 1-4. Synthesis of [Formula 3]. Under nitrogen atmosphere, [intermediate 1-c] 14.4 g (26.7 mmol), 4-tert-butyldiphenylamine 6.0 g (26.7 mmol), bis(benzyl)acetone dipalladium 0.4 g (0.7 mmol), bis(benzyl)acetone dipalladium 0.4 g (0.7 mmol), bis(b)bphthalate (BINAP) 0.7 g (1 mmol), sodium tert-butanol 6.5 g (66.9 mmol), toluene 100 mL after 12 hours of reflux. At the end of the reaction, the layers were separated and the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain [chemical formula 3] 14.8g. (Yield 67%)

Reference： [1]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - CN109790462, 2022, B Location in patent: Paragraph 0159; 0169-0172

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CAS No. :	4496-49-5	MDL No. :	MFCD00443884
Formula :	C₁₆H₁₉N	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	UOMXLEWVJZEVGP-UHFFFAOYSA-N
M.W :	225.33	Pubchem ID :	11447459
Synonyms :

Num. heavy atoms :	17
Num. arom. heavy atoms :	12
Fraction Csp3 :	0.25
Num. rotatable bonds :	3
Num. H-bond acceptors :	0.0
Num. H-bond donors :	1.0
Molar Refractivity :	75.26
TPSA :	12.03 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	Yes
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.03 cm/s

Log Po/w (iLOGP) :	3.06
Log Po/w (XLOGP3) :	5.14
Log Po/w (WLOGP) :	4.73
Log Po/w (MLOGP) :	4.38
Log Po/w (SILICOS-IT) :	3.98
Consensus Log Po/w :	4.26

[ CAS No. 4496-49-5 ] {[proInfo.proName]}

Quality Control of [ 4496-49-5 ]

Related Doc. of [ 4496-49-5 ]

Product Details of [ 4496-49-5 ]

Calculated chemistry of [ 4496-49-5 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4496-49-5 ]

Application In Synthesis of [ 4496-49-5 ]

[ 4496-49-5 ] Synthesis Path-Upstream 1~2

[ 4496-49-5 ] Synthesis Path-Downstream 1~84

Related Functional Groups of
[ 4496-49-5 ]

Aryls

Amines

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

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

Log S (ESOL) :	-4.8
Solubility :	0.00357 mg/ml ; 0.0000159 mol/l
Class :	Moderately soluble
Log S (Ali) :	-5.14
Solubility :	0.00164 mg/ml ; 0.00000728 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-6.18
Solubility :	0.000148 mg/ml ; 0.000000656 mol/l
Class :	Poorly soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	1.73

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

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

[ CAS No. 4496-49-5 ] {[proInfo.proName]}

Quality Control of [ 4496-49-5 ]

Related Doc. of [ 4496-49-5 ]

Product Details of [ 4496-49-5 ]

Calculated chemistry of [ 4496-49-5 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4496-49-5 ]

Application In Synthesis of [ 4496-49-5 ]

[ 4496-49-5 ] Synthesis Path-Upstream 1~2

[ 4496-49-5 ] Synthesis Path-Downstream 1~84

Related Functional Groups of [ 4496-49-5 ]

Aryls

Amines

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 4496-49-5 ]