Name: 135-67-1|10H-Phenoxazine|98%
Brand: Ambeed
SKU: A129838
Price: 5.0 USD
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1
[ 6192-43-4 ]
[ 135-67-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sodium methylate Inert atmosphere;
69%	Stage #1: 1-(10H-phenoxazin-10-yl)ethan-1-one With Triethoxysilane; sodium triethylborohydride In tert-butyl methyl ether at 80℃; for 24h; Stage #2: With hydrogenchloride In tert-butyl methyl ether; water at 20℃; for 1h; chemoselective reaction;
63%	With triethyl borane; sodium hydroxide In tert-butyl methyl ether at 80℃; for 6h; Inert atmosphere; Sealed tube;	10 Example 10, wherein the amide substrate is as follows: Under argon atmosphere,Firstly, NaOH and triethylboron are stirred to form a transparent clear solution at room temperature.The concentration is 1M/L;Then,The above triethylboron solution was successively treated with 10umol (2mol%),Amide substrate 5mmol,Triethoxysilane or polymethylhydrogensiloxane 15mmol,MTBE 2mL added to the 10mL sealed tube,It is heated and stirred in an 80°C oil bath for 6 hours.The reaction is over,Exposing the reaction to air quenching,The amine product is then separated directly by column chromatography.According to the results of column chromatography separation, when using triethoxysilane or polymethylhydrogensiloxane (PMHS),The yield of the target product was:

	With sulfuric acid
	Multi-step reaction with 2 steps 1: potassium hydroxide; triethyl borane / tetrahydrofuran / 24 h / 25 °C / Inert atmosphere; Schlenk technique; Sealed tube 2: sodium hydroxide; water / tetrahydrofuran / 1 h / 25 °C / Inert atmosphere; Schlenk technique; Sealed tube

Reference： [1]Location in patent: scheme or table Thome, Isabelle; Bolm, Carsten [Organic Letters, 2012, vol. 14, # 7, p. 1892 - 1895]
[2]Yao, Wubing; Li, Rongrong; Yang, Jianguo; Hao, Feiyue [Catalysis science and technology, 2019, vol. 9, # 15, p. 3874 - 3878]
[3]Current Patent Assignee: TAIZHOU UNIVERSITY - CN107337573, 2017, A Location in patent: Paragraph 0054; 0055; 0056; 0057
[4]Kehrmann; Boubis [Chemische Berichte, 1917, vol. 50, p. 1663]
[5]Li, Jinshan; Wang, Jiali; Yang, Jianguo; Yao, Wubing; Zhong, Aiguo [Organic Letters, 2020, vol. 22, # 20, p. 8086 - 8090]

2
[ 135-67-1 ]
[ 591-50-4 ]
[ 37832-25-0 ]

Yield	Reaction Conditions	Operation in experiment
87%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 24h; Inert atmosphere; Reflux;	20 Example 20 M 15 synthetic: under the protection of the argon, will phenoxazin (10mmol, 1 . 83g), iodophenylamino (15mmol, 3 . 06g) in 250 ml of the three-port in the reaction bottle, by adding 100 ml of toluene to dissolve them. After dissolving, butyl sodium alcoholate joins uncle sequentially (4.8g, 50mmol), three extra butyl phosphine (0.5 ml, 1M/L) and palladium acetate (112 mg, 0 . 5mmol), system is greenish black. After finishing the feeding, heating to 110 °C, reflux, reaction 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the white solid 2.25g, yield 87%.
	With copper; potassium carbonate

Reference： [1]Current Patent Assignee: SOUTH CHINA UNIVERSITY OF TECHNOLOGY - CN105254562, 2016, A Location in patent: Paragraph 0019; 0020; 0121; 0124
[2]Gilman; Moore [Journal of the American Chemical Society, 1957, vol. 79, p. 3485]

3
[ 135-67-1 ]
[ 583-55-1 ]
[ 131013-62-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	With copper(l) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene for 48h; Reflux; Inert atmosphere;	1.1 step 1 4.23 g of o-bromoiodobenzene was dissolved in 80 mL of o-dichlorobenzene under argon atmosphere, then 1.83 g of phenoxazine, 0.7 g of cuprous iodide, 0.1 g of 18 crown 6 ether and 5.0 g of potassium carbonate were added sequentially into 200 ml the reaction flask. After refluxing for 48 hours under argon gas, the reaction solution was cooled to room temperature. The solvent was removed by rotary evaporator. The reaction solid was dissolved in 80 mL of dichloromethane and the organic layer was washed three times with 50 mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying with silica gel was passed through a column of dichloromethane / petroleum ether = 3: 7 (volume ratio), and then dried to give 3.04 g of 2-bromooxatriphenylamine in a yield of 90%. Step 2: 1.52 g of 2-bromooxatriphenylamine was dissolved in 80 mL of tetrahydrofuran under argon atmosphere, cooled to -78 ° C, and 2.38 mL of n-butyllithium was slowly added into the solution through a constant pressure dropping funnel and reacted for 1 hour. Then, 1.3 g of 2-Bromo-9-fluorenone was dissolved in 40 mL of tetrahydrofuran under argon gas and added dropwise to the reaction liquid. After 1 hour of low temperature reaction, the temperature was gradually raised to room temperature. After 12 hours of reaction, 5 mL of water was added to the reaction, and then the solvent was spin-dried under reduced pressure. The solid was dissolved in 80 mL of dichloromethane and the organic layer was washed three times with 50 mL of water. The organic layer was dried over anhydrous sodium sulfate and then spin-dried. The solid obtained by spin-drying was dissolved in 45 mL of glacial acetic acid and 10 mL of nicotinic acid, refluxed for 4 hr, and then cooled to room temperature, then filtered and washed three times with petroleum ether. The obtained solid was passed through a column of dichloromethane / petroleum ether = 4: 6 (volume ratio), and dried to give 2.1 g of 2-bromo oxacyclo spirofluorene triphenylamine in a yield of 84%.
84.64%	With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In 5,5-dimethyl-1,3-cyclohexadiene at 135 - 145℃; for 12h;	1.1 (1) Preparation of intermediate I in 1 L bottle in three, adding OLEDs (36.6 g, 0 . 20 µM), O-[...] (62.2 g, 0 . 22 µM), tertiary butyl alcohol sodium (28.8 g, 0 . 30 µM), palladium acetate (0.45 g, 2.0 mmol), P (t - Bu)3HBF4(1.16 G, 4 mmol) and 500 ml xylene, 135 - 145 °C reaction 12 h, after the reaction, the reaction system is added in 200 g water quenching reaction, filtration, filtrate desolventizing, column chromatography purification, then toluene, petroleum ether recrystallization to obtain the intermediate I, yield 84.64%
78%	With bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene for 3h; Inert atmosphere; Reflux;	2 Combine X012 (3.2mmol), X013 (3.4mmol), (dibenzylideneacetone) two palladium (0) (0.30mmol), sodium tert-butoxide (4.5mmol), tri-tert-butylphosphine tetrafluoroborate (0.6mmol) ) Put it into a 250mL three-necked flask, and while stirring, quickly repeat degassing and nitrogen replacement 3 times, and add 80mL toluene through a syringe.The mixture was heated to reflux for 3 hours under a stream of nitrogen.After the reaction, water was added to the reaction solution that was left to cool to room temperature, extracted with dichloromethane, and washed with saturated brine.After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off, and it was purified by column chromatography to obtain intermediate X014 (2.5 mmol, 78%).

78%	With bis(tri-t-butylphosphine)palladium⁽⁰⁾; sodium t-butanolate In toluene Reflux;	1.1-1 Step 1-1: Preparation of intermediate compound 1-1 10H-phenoxazine (16.0 g, 87.3 mmol), 1-bromo-2-iodobenzene (24.71 g, 87.3 mmol), Pd(t-Bu3P)2 (0.45 g, 0.9 mmol), NaOt-Bu (25.18 g, 96.1 mmol) was dissolved in toluene (290 ml) and stirred under reflux. When the reaction was completed, the mixture was cooled to room temperature, and the reaction product was transferred to a separatory funnel and extracted. Thereafter, dried over MgSO 4, filtered, concentrated, and purified by column chromatography to obtain an intermediate compound 1-1 (23.04 g, yield 78%).
72%	With copper; potassium hydroxide at 200℃; for 3h;	8 Synthesis Example 8: Synthesis of Intermediate 1-8 In a 0.5 L flask, phenoxazine (20 g, 0.145 mol), potassium hydroxide (60 g, 0.434 mol), copper (9.2 g, 0.22 mol) and 1-bromo-2-iodobenzene (160 g, 0.56 mol) were placed, and the result was refluxed at 200° C. After approximately 3 hours, the result was cooled to room temperature, filtered to remove copper, and then the filtrate was extracted with ammonia water and ethyl acetate. The obtained organic layer was filtered by being treated with anhydrous magnesium sulfate and activated carbon, and then concentrated. The result was recrystallized with ethyl acetate and normal hexane to obtain (35.2 g, yield 72%).
64%	With copper; potassium carbonate In nitrobenzene at 210℃; for 12h; Inert atmosphere;	5.1 <Step 1> Synthesis of 10- (2-bromophenyl) -10H-phenoxazine Under a nitrogen stream, 10H-phenoxystyrene (100 g, 545.8 mmol),1-Bromo-2-iodobenzene (185.3 g, 655.0 mmol),Cu (17.3 g, 272.9 mmol),K2CO3 (150.9 g, 1091.6 mmol)And nitrobenzene (2000 ml) were mixed and stirred at 210 for 12 hours.After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO4,Purification by column chromatography (Hexane: EA = 10: 1 (v / v)) gave 10- (2-bromophenyl) -10H-phenoxazine (118.1 g, yield 64%).
	With copper; potassium carbonate
	With potassium carbonate; copper(II) sulfate In 1,2-dichloro-benzene

Reference： [1]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN108250214, 2018, A Location in patent: Paragraph 0046-0047
[2]Current Patent Assignee: VALIANT CO., LTD. - CN108358950, 2018, A Location in patent: Paragraph 0056; 0057; 0058
[3]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN111848642, 2020, A Location in patent: Paragraph 0098; 0107-0109
[4]Current Patent Assignee: LG CHEM CO.,LTD. - KR2020/136713, 2020, A Location in patent: Paragraph 0201-0205
[5]Current Patent Assignee: LG CHEM CO.,LTD. - US11201293, 2021, B2 Location in patent: Page/Page column 92
[6]Current Patent Assignee: DOOSAN CORP. - KR2018/71881, 2018, A Location in patent: Paragraph 0284-0288
[7]Gilman; Moore [Journal of the American Chemical Society, 1957, vol. 79, p. 3485]
[8]Hong, Jong-In; Huh, Jin-Suk; Yang, Dongwook [Dyes and Pigments, 2022, vol. 197]

4
[ 135-67-1 ]
[ 13338-49-3 ]
[ 14169-51-8 ]

Reference： [1]Patent: DE842943,1951,
DRP/DRBP Org.Chem.,

5
[ 135-67-1 ]
[ 109-70-6 ]
[ 92425-82-6 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: phenoxazine With n-butyllithium In tetrahydrofuran; hexane; toluene at -78 - 0℃; for 1.5h; Inert atmosphere; Stage #2: 1.3-chlorobromopropane In tetrahydrofuran; hexane; toluene Reflux; Inert atmosphere;	Modified method A, reactant: 36. To a cold (-78 °C) solution of 36 (0.75 g, 4.09 mmol) in THF/toluene(3:2 (v/v), 50 mL), n-BuLi (3.07 mL, 4.91 mmol) was added over a period of 30 min under argon atmosphere. After stirring 1 h at 0 °C, 100 (0.48 mL, 4.91 mmol) in 5 mL toluene was added, stirred 1h at RT and then refluxed overnight. The mixture was cooled to RT, diluted with toluene (50 mL), washed with 1N-HCl (10 mL) and brine (10 mL); the organic layer was dried with Na2SO4 and concentrated to give a yellow solid: 106 (0.94 g, 88 %).
	With sodium amide In ammonia
	With ammonia; sodium amide 1.) 30 min, 2.) 1 h; Yield given. Multistep reaction;

	In ammonia; water	1 EXAMPLE 1 EXAMPLE 1 10-(3'-chloropropyl)-phenoxazine. To a suspension of sodium amide (1.72 g) in 100 ml of liquid ammonia, 7 g (0.038 mol) of phenoxazine was added. After stirring for 30 minutes, 6.3 g (0.04 mol., 3.96 mL) of 1-bromo-3-chloropropane was added slowly with constant stirring. After one more hour, ammonia was allowed to evaporate and solid ice pieces were added carefully followed by cold water. When the reaction ceased, the mixture was extracted three times with ether. The ether solution was washed three times with water, dried over anhydrous sodium sulfate and evaporated. The residue was chromatographed on silica gel. Petroleum ether-ethylacetate (9 mL+3 mL) eluted the pure title compound (7.94 g) as white crystals. VU-λmax (MeOH) 218, 238 and 321 nm; IR (KBr) 3070, 2860, 1630, 1490, 1380, 1275, 920, 815 and 740 cm-1; 1 H-NMR (δ) 6.47-6.82 (m, 8H, ArH, H1 -H4 and H6 -H9), 2.11 (m, 2H, H1), 3.63 (m, 2H, HK), and 3.69 (m, 2H, Hm); 13 C-NMR (1 H decoupled) 111.23 (C1 and C9), 115.50 (C4 and C6), 121.07 (C3 and C7), 123.70 (C2 and C8), 133.03 (C1' and C9'), 144.92 (C4' and C6'), 27.82 (C1), 41.09 (CK) and 42.63 (Cm); EIMS (m/z) 259 (M+).
	With ammonium chloride In <i>N</i>-methyl-acetamide	9 (R)-1-(3-(10H-Phenoxazin-10-yl)-1-propyl)-3-piperidinecarboxylic acid hydrochloride Example 9 (R)-1-(3-(10H-Phenoxazin-10-yl)-1-propyl)-3-piperidinecarboxylic acid hydrochloride To a solution of phenoxazine (3.7 g, 0.02 mol) in dry dimethylformamide (100 ml) kept under an atmosphere of nitrogen, sodium hydride (1.2 g, 0.03 mol, 60% dispersion in oil) was carefully added. The reaction mixture was left stirring for 15 minutes. 1-Bromo-3-chloro-propane (8.0 g, 0.05 mol) was added and the mixture was left stirring overnight. Ammonium chloride (2.0 g, 0.04 mol) was added, and after continued stirring for 30 minutes, the solution was poured onto water (300 ml). The mixture was extracted with dichloromethane (2*200 ml). The combined organic extracts were dried (MgSO4), filtered and the solvent evaporated in vacuo. 10-(3-Chloropropyl)-10H-phenoxazine was obtained in quantitative yield as an oil and used without further purification. Rf: 0.68 (SiO2; n-heptane/ethyl acetate=1:1).
	Stage #1: phenoxazine With ammonia; sodium for 1h; Stage #2: 1.3-chlorobromopropane at 20℃;	A dry two-necked 250 ml round bottom flask containing about 75 ml of dry liquid ammonia and fitted with a stirring bar ammonia condenser and calcium chloride guard tube was charged with phenoxazine (3.5g). Initially few sodium pieces were added carefully then Ferric chloride in catalytic amount was added. This was followed by further addition of sodium pieces, after stirring for about 1 hour, bromochloropropane was added drop wise. The reaction mixture was then allowed to come to room temperature slowly overnight. To the residue, water was added and extracted with ether. Ether extract was washed with water, and brine, dried over anhydrous sodium sulfate, concentrated in vacuo to form 10-(3-chloropropyl)-10H-phenoxazine Yield: 4.7g.

Reference： [1]Blaess, Markus; Bibak, Nelly; Claus, Ralf A.; Kohl, Matthias; Bonaterra, Gabriel A.; Kinscherf, Ralf; Laufer, Stefan; Deigner, Hans-Peter [European Journal of Medicinal Chemistry, 2018, vol. 153, p. 73 - 104]
[2]Gal,A.E.; Avakian,S. [Journal of Medicinal Chemistry, 1963, vol. 6, p. 809 - 811]
[3]Thimmaiah, Kuntebommanahalli N.; Horton, Julie K.; Seshardi, Ramakrishnan; Israel, Mervyn; Houghton, Janet A.; et al. [Journal of Medicinal Chemistry, 1992, vol. 35, # 18, p. 3358 - 3364]
[4]Current Patent Assignee: ST. JUDE CHILDRENS RESEARCH HOSPITAL - US5371081, 1994, A
[5]Current Patent Assignee: NOVO NORDISK A/S - US5741791, 1998, A Current Patent Assignee: NOVO NORDISK A/S - US5595989, 1997, A
[6]Current Patent Assignee: SUN PHARMACEUTICAL INDUSTRIES LIMITED - WO2006/117760, 2006, A1 Location in patent: Page/Page column 55

6
[ 135-67-1 ]
[ 4181-20-8 ]
4,4',4''-Tri(N-phenoxazinyl)triphenylamine [ No CAS ]

Reference： [1]Molecular Crystals and Liquid Crystals Science and Technology, Section A: Molecular Crystals and Liquid Crystals,1994,vol. 242,p. 127 - 134

7
[ 135-67-1 ]
[ 52853-40-4 ]
N-[(2,4-diaminopteridin-6-yl)methyl]phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34%		EXAMPLE 4; Preparation of N-[(2,4-Diaminopteridin-6-yl)methyl]phenoxazine (Formula I: Ar=6-(2,4-diaminopteridine); X=N; W=CH2; Z=O; m=n=0);.NaH (60% oil suspension containing 51 mg, 2.0 mmol) was added to a stirred solution of phenoxazine (147 mg, 0.784 mmol) in dry THF (10 mL) at 0 C. under N2. After 10 min. 2,4-diamino-6-bromomethylpteridine hydrobromide (100 mg, 0.392 mmol) was added and the reaction mixture was allowed to come to room temperature and left to stir for 2 days. The excess NaH was decomposed with MeOH (1 mL), and the mixture was concentrated to dryness by rotary evaporation. Flash chromatography on silica gel yielded the title compound, N-[(2,4-diaminopteridin-6-yl)methyl]phenoxazine, as a brown solid; yield 47 mg (34%); mp >250 C. dec. Anal. Calcd. for C19H15N7O0.4H2O: C, 62.60; H, 4.37. Found: C, 62.84; H, 4.10.

Reference： [1]Journal of Medicinal Chemistry,1999,vol. 42,p. 4853 - 4860
[2]Patent: US7056911,2006,B1 .Location in patent: Page/Page column 13; 18

8
[ 63837-11-6 ]
[ 135-67-1 ]
[ 556836-62-5 ]

Reference： [1]Tetrahedron,2003,vol. 59,p. 3109 - 3116

9
[ 135-67-1 ]
3,7-dibromo-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With N-Bromosuccinimide In N,N-dimethyl-formamide for 10h; Cooling with ice;	5.1 (1) Synthesis of intermediate 10: The phenoxazine (44.0 g, 0.24 mol) was dissolved in 250 ml of DMF and cooled in an ice water bath. Subsequently, NBS (85.2 g, 0.48 mol) was dissolved in 150 ml of DMF, and the mixture was slowly added dropwise thereto for 10 hours.After the reaction was completed, the reaction mixture was poured into a large amount of water and filtered to give a white solid.After vacuum drying the white solid,Column separation and purification with petroleum ether: dichloromethane (10:1) gave 89.5 g of product.
80%	With N-Bromosuccinimide In chloroform at 20℃; for 2h;
80%	With N-Bromosuccinimide In N,N-dimethyl-formamide for 12h; Cooling with ice;	11.1 (1) Synthesis of Intermediate 27: Phenoxazine (50.0 g, 272.91 mmol) was dissolved in 250 ml DMF and cooled in an ice water bath. Subsequently, NBS (97.2 g, 545.85 mmol) was dissolved in 120 ml DMF, slowly added dropwise, and the reaction was continued for 12 h.After the reaction is complete, pour the reaction liquid into a large amount of water,Filter to obtain a white solid. After drying it in vacuum,Carry out column separation and purification with petroleum ether: dichloromethane (10:1),27 was obtained as a white solid (74.4 g, 80%).

10%	Stage #1: phenoxazine With hydrogen bromide In acetone at 20℃; for 15h; Stage #2: With sodium nitrite In acetone at 20℃; for 0.25h;
10%	Stage #1: phenoxazine With hydrogen bromide In water; acetone at 20℃; for 0.25h; Stage #2: With sodium nitrite In water; acetone at 20℃; for 0.25h;	1.3 1.3 Synthesis of 3,7-Dibromophenoxazine (3) Concentrated hydrobromic acid (48% in water, 30 mL) was added to a solution of phenoxazine (2.01 g, 11 mmol) in acetone (17.5 mL) and the resulting purple-colored reaction mixture was stirred at room temperature for 15 min. A saturated aqueous solution of sodium nitrite (2.02 g, 29 mmol) was added dropwise to the mixture over a period of 3 min, and the reaction was stirred at room temperature for an additional 15 min. The resulting precipitate was filtered off, washed with water (200 mL), and redissolved in hot acetone (200 mL). The acetone was removed by rotary evaporation to leave a dark purple residue, which was purified by flash column chromatography (silica gel, 3:1 hexanes/ethyl acetate) to afford dibromo 3 as a metallic blue solid (375 mg, 10% yield). 1H NMR (d6-acetone, 300 MHz): δ 6.90 (2H, dd, J1=8.1 Hz, J2=2.1 Hz), 6.79 (2H, s), 6.46 (2H, d, J=8.4 Hz). HRFAB-MS: calculated for [M+] 338.889, found 338.889.
	With concentrated hydrobromic acid; sodium nitrite In water; acetone	1.3 1.3 1.3 Synthesis of 3,7-Dibromophenoxazine (3) Concentrated hydrobromic acid (48% in water, 30 mL) was added to a solution of phenoxazine (2.01 g, 11 mmol) in acetone (17.5 mL) and the resulting purple-colored reaction mixture was stirred at room temperature for 15 min. A saturated aqueous solution of sodium nitrite (2.02 g, 29 mmol) was added dropwise to the mixture over a period of 3 min, and the reaction was stirred at room temperature for an additional 15 min. The resulting precipitate was filtered off, washed with water (200 mL), and redissolved in hot acetone (200 mL). The acetone was removed by rotary evaporation to leave a dark purple residue, which was purified by flash column chromatography (silica gel, 3:1 hexanes/ethyl acetate) to afford dibromo 3 as a metallic blue solid (375 mg, 10% yield). 1H NMR (d6-acetone, 300 MHz): δ 6.90 (2H, dd, J1=8.1 Hz, J2=2.1 Hz), 6.79 (2H, s), 6.46 (2H, d, J=8.4 Hz). HRFAB-MS: calculated for [M+] 338.889, found 338.889.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN109970796, 2019, A Location in patent: Paragraph 0126-0128
[2]Weber, Maria; MacKenzie, Amanda B.; Bull, Steven D.; James, Tony D. [Analytical Chemistry, 2018, vol. 90, # 17, p. 10621 - 10627]
[3]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN111548342, 2020, A Location in patent: Paragraph 0139-0142
[4]Miller, Evan W.; Albers, Aaron E.; Pralle, Arnd; Isacoff, Ehud Y.; Chang, Christopher J. [Journal of the American Chemical Society, 2005, vol. 127, # 47, p. 16652 - 16659]
[5]Current Patent Assignee: UNIVERSITY OF CALIFORNIA - US8791258, 2014, B2 Location in patent: Page/Page column 52
[6]Current Patent Assignee: UNIVERSITY OF CALIFORNIA - US2011/130306, 2011, A1

10
[ 63996-36-1 ]
[ 135-67-1 ]
[ 947192-79-2 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃;	967 mg (4.10 mmoL) of Compound J, 759 mg (4.14 mmoL) of phenoxazine, 28 mg (0.123 mmoL) of Pd(OAc)2, 99 mg (0.492 mmoL) of P(t-Bu)3, and 569 mg (5.92 mmoL) of NaOt-Bu are dissolved in 40 mL of toluene, and the mixture is heated to 110 C., and the temperature is maintained until the reaction is terminated. When the reaction is terminated, the resultant is subjected to a work-up procedure and column chromatography to obtain Compound K (yield: 80%).

Reference： [1]European Journal of Inorganic Chemistry,2006,p. 3676 - 3683
[2]Patent: KR101594129,2016,B1 .Location in patent: Paragraph 0220; 0226-0227

11
[ 5165-28-6 ]
[ 135-67-1 ]
[ 56820-75-8 ]

Yield	Reaction Conditions	Operation in experiment
	With trichlorophosphate;	EXAMPLE 3 Reaction of phenoxazine, <strong>[5165-28-6]5,5-dimethyl-2-pyrrolidinone</strong> and phosphorus oxychloride according to the procedure of Example 1 provides the free base 10-(5,5-DIMETHYL-1-PYRROLIN-2-YL)-PHENOXAZINE, m.p. 148-150C.

Reference： [1]Patent: US3962252,1976,A

12
[ 135-67-1 ]
[ 5111-65-9 ]
[ 944358-45-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium t-butanolate In toluene at 80℃; for 12h;	1 SYNTHESIS EXAMPLE 1; According to a reaction path of Reaction Scheme 1, compound 19 represented by Formula 19 was synthesized: Synthesis of Compound 19; Synthesis of Intermediate A; 7.5 g (32 mmol) of 2-bromo-6-methoxynaphthalene, 4.6 g (25 mmol) of phenoxazine, 3.7 g (38 mmol) of sodium tert-butoxide ((t-BuO)Na), 0.3 g (0.33 mmol) of Pd2(dba)3 [(tris(dibenzylidine acetone) dipalladium (0))], and 0.11 g (0.55 mmol) of tri(tert-butyl)phosphine were dissolved in 125 mL of toluene and were reacted for 12 hours at 80° C.After the reaction was completed, the reaction mixture was cooled down to an ambient temperature and 200 ml of distilled water was added and quenched. Then, xylene and water were extracted in the volume ratio of 1:1.The collected organic layer was dried and concentrated using MgSO4 and a column chromatography was performed using an eluant formed of toluene and hexane in the volume ratio of 1:2. The obtained effluent was concentrated and dried to obtain 6.8 g (Yield: 80%) of intermediate A. The structure of intermediate A was identified through 1H NMR spectroscopy.

Reference： [1]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US2007/176541, 2007, A1 Location in patent: Page/Page column 12-13

13
[ 104-92-7 ]
[ 135-67-1 ]
[ 58736-67-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;
85.7%	With tri-tert-butyl phosphine; palladium diacetate; sodium tertiary butoxide In toluene at 20 - 110℃; for 24h; Inert atmosphere;	1.i (i) adding p-methoxybromobenzene (0.823 g, 4.40 mmol) to a dry reaction vessel,Phenothiazine (0.732 g, 4.00 mmol), catalyst palladium acetate (0.018 g, 0.08 mmol),Tri-tert-butylphosphine (5% mmol), sodium tert-butoxide (0.577 g, 6.00 mmol)And solvent toluene (50mL), under nitrogen protection and stirring at room temperature,It was then heated to 110 ° C for 24 h.After the reaction was completed, it was cooled to room temperature, and 50 mL of dichloromethane was added to the reaction solution.Wash three times with 150 mL of water, collect the organic layer, and remove the solvent under reduced pressure.The residue was separated and purified on a silica gel column.Petroleum ether/dichloromethane (4:1 vol/vol) as eluent, dried under vacuum,Compound 1 (0.991 g, yield: 85.7%) was obtained as white solid.
85.18%	With tri-tert-butyl phosphine; palladium diacetate; sodium tertiary butoxide In toluene at 85℃; for 14h;	S11 Add 2.00g phenoxazine (reaction monomer 1), 0.45ml p-bromoanisole (reaction monomer 2), 0.27g palladium acetate (catalyst) and 2.97g sodium tert-butoxide (pH adjustment Agent, adjust the PH to alkaline, assist the catalytic cycle). Then seal and connect the condenser tube and the double-row tube, and after removing the oxygen in the two-necked bottle by pumping 4 times, add 2.30 mL of tri-tert-butyl phosphine (catalyst ligand) and dissolve it in the toluene solvent (the content of tri-tert-butyl phosphine) (Accounting for 10% of toluene content), then add 170mL of ultra-dry toluene (reaction solvent). Then the reaction system was raised to 85°C, and after 14 hours of reaction, it was naturally cooled to room temperature. The liquid was separated and extracted by adding water and dichloromethane, then dried with anhydrous magnesium sulfate, filtered under reduced pressure, and the solution was concentrated by rotary evaporation and then purified. Intermediate 1 is obtained, wherein the yield of Intermediate 1 is 2.68 g, and the yield is 85.18%. The reaction principle for the specific formation of Intermediate 1 can be referred to reaction formula (1).

80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 110℃; for 16h; Schlenk technique; Inert atmosphere;	2.1 ((1) To a 50 mL Schlenk reaction tube, add phenoxazine (1.1 g, 6 mmol), 1-bromo-4-methoxybenzene (1.23 g, 6.6 mmol), Pd2dba3 (27 mg, 0.03 mmol), t-Bu3PHBF4 ( 35 mg, 0.12 mmol, tri-tert-butylphosphine tetrafluoroborate), sodium tert-butoxide (900 mg, 6 mmol) and anhydrous toluene (10 mL, PhMe), and then three times of pumping, and reacting at 110 ° C under nitrogen atmosphere 16 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography (petroleum ether:ethyl acetate=25:1 as eluent),10-(4-Methoxyphenyl)-10H-phenoxazine (1.39 g, 80% yield) was obtained as a white solid.
72%	With tri-tert-butyl phosphine; sodium tertiary butoxide In toluene for 15h; Reflux;	4 Synthesis Example 4Synthesis of Intermediate DAn intermediate D was synthesized according to Reaction Scheme 3 below: Phenoxazine (2.00 g, 10.92 mmol), 4-bromoanisole (2.25 g, 12.03 mmol), Pd2(dba)3 (0.10 g, 0.11 mmol), t-Bu3P (0.067 g, 0.33 mmol), and t-BuONa (1.57 g, 16.34 mmol) were dissolved in toluene (100 ml), and the reaction mixture was refluxed for 15 hours and cooled to room temperature. The solvent was removed under reduced pressure, and the residue was extracted with chloroform. The extracted solution was twice washed with a supersaturated sodium chloride solution and water (H2O), and the organic layer was collected and dried over anhydrous magnesium sulfate. The solvent was evaporated to obtain a crude product, and the crude product was purified by silica gel column chromatography to yield 2.27 g (72%) of a compound where the N-position of phenoxazine was substituted by anisole. The compound (2.00 g, 6.91 mmol) was dissolved in chloroform (100 ml), and acetic acid (100 ml) was added thereto. N-bromosuccinimide (NBS) (2.70 g, 15.20 mmol) was added in small amounts at 0° C., and the reaction mixture was heated to room temperature and incubated at room temperature for 10 hours. After the reaction was terminated, the solvent was removed under reduced pressure, and the residue was extracted with chloroform. The extracted solution was twice washed with a supersaturated sodium chloride solution and water (H2O), and the organic layer was collected and dried over anhydrous magnesium sulfate. The solvent was evaporated to obtain a crude product, and the crude product was purified by silica gel column chromatography to yield 2.62 g (85%) of a phenoxazine derivative compound substituted by a dibromo compound. The phenoxazine derivative compound (1.47 g, 3.29 mmol) was dissolved in tetrahydrofuran (100 ml), and n-butyllithium (4.6 ml, 7.36 mmol, 1.6 M solution) and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.48 ml, 7.25 mmol) were gradually dropwise added thereto at -78° C. The reaction mixture was gradually heated to room temperature and incubated at room temperature for 15 hours. The reaction was terminated by the addition of water (H2O) (50 ml), and the resultant solution was extracted with chloroform. The extracted solution was twice washed with a supersaturated sodium chloride solution and water (H2O), and the organic layer was collected and dried over anhydrous magnesium sulfate. The solvent was evaporated to obtain a crude product, and the crude product was purified by silica gel column chromatography to yield 1.16 g (65%) of the intermediate D.

Reference： [1]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[2]Current Patent Assignee: JIANGSU UNIVERSITY - CN109265410, 2019, A Location in patent: Paragraph 0043-0046
[3]Current Patent Assignee: BOE TECHNOLOGY GROUP CO., LTD. - CN113527279, 2021, A Location in patent: Paragraph 0112-0115
[4]Current Patent Assignee: UNIV SOUTH CHINA NORMAL - CN114133385, 2022, A Location in patent: Paragraph 0090-0094
[5]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US7718278, 2010, B2 Location in patent: Page/Page column 21-22

14
[ 135-67-1 ]
[ 50638-46-5 ]
[ 1380485-60-8 ]

Yield	Reaction Conditions	Operation in experiment
57%	With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; at 75℃; for 2h;Inert atmosphere;	(Example 1) Synthesis of Exemplified Compound IPlOl [0100] [0101] (1) Synthesis of intermediate IP-OMe The following reagents and solvent were loaded into a 300-mL recovery flask. Phenoxazine: 8.00 g (43.7 mmol) 4-Bromo-3-chloroanisole : 9.21 g (41.6 mmol) Tris (dibenzylidene) bispalladium: 1.14 g (1.25 mmol) Tri-tert-butylphosphine : 0.76 g (3.76 mmol) . . tert-Butoxysodium: 5.99 g (62.4 mmol) Toluene: 160 mL [0102] Next, the reaction solution was heated at 75C for 2 hours with stirring under nitrogen. After the completion of the reaction, the reaction solution was washed with water, dried over sodium sulfate, and then concentrated under reduced pressure to give a crude product. Next, the resultant crude product was purified by silica gel column chromatography (eluent: heptane/toluene=4/l) to afford 7.60 g of 10- (2-chloro- 4-methoxyphenyl) phenoxazine (yield: 57%).[ 0103 ] Subsequently, the following reagents were loaded into a 300-mL recovery flask, and gas in the recovery flask was replaced by nitrogen. 10- (2-Chloro-4-methoxyphenyl) phenoxazine : 7.60 g (23.5 mmol) Palladium acetate: 317 mg (1.41 mmol) Tricyclohexylphosphonium tetrafluoroborate : 1.04 g (2.82 mmol) Potassium carbonate: 6.49 g (46.9 mmol)[0104] ext, 150 mL of N, N-dimethylacetamide, into which nitrogen had been bubbled, were added. The reaction solution was then heated at 135C for 6 hours with stirring under nitrogen. After the completion of the reaction, the reaction solution was filtered by short silica gel column chromatography (eluent: heptane/ethyl acetate=10/l) . The filtrate was then concentrated under reduced pressure to give a crude product. Next, the resultant crude product was purified by silica gel column chromatography (eluent: heptane/toluene=2/l) to afford 6.16 g of an intermediate IP-OMe (yield: 91%).[ 0105 ] Further, the resultant compound was identified by 1H- NMR measurement. [1H-N R (400 MHz, CDC13) ] delta 7.77 (d, 1H), 7.56 (dd, 1H) , 7.48 (d, 1H) , 7.38 (d, 1H) , 7.13 (dd, 1H) , 7.05-6.90 (m, 4H) , 6.68 (d, 1H) , 3.93 (s, 3H) .

Reference： [1]Patent: WO2012/77582,2012,A1 .Location in patent: Page/Page column 34-35

15
[ 135-67-1 ]
[ 57381-62-1 ]
[ 1380170-32-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium carbonate; sodium sulfate;copper; In nitrobenzene; at 220℃; for 7h;Inert atmosphere;	The following reagents and solvent were loaded into a reactor.10H-Phenoxazine: 10.0 g (54.58 mmol)Methyl 2-bromo-4-chlorobenzoate : 15.12 g (60.65 mmol) Copper: 3.85 g (60.65 mmol)Potassium carbonate: 8.38 g (60.65 mmol)Sodium sulfate: 8.61 g (60.65 mmol)Nitrobenzene: 125 ml [0110] Next, the reaction solution was stirred with heating under nitrogen at 220°C for 7 hours. After the completion of the reaction, the reaction solution was concentrated under reduced pressure. To the resultant residue was added ethyl acetate, and the mixture was then washed with an aqueous solution of ammonium chloride. The organic layer was concentrated under reduced pressure to give a crude product. Next, the resultant crude product was purified by columnchromatography (silica gel) to afford 15.9 g of methyl 5-chloro-2- ( lOH-phenoxazin-10-yl ) benzoate (yield: 83percent)

Reference： [1]Patent: WO2012/73679,2012,A1 .Location in patent: Page/Page column 35

16
[ 135-67-1 ]
[ 627-32-7 ]
[ 27874-59-5 ]

Yield	Reaction Conditions	Operation in experiment
73%		The reaction of phenoxazine (500 mg, 2.729 mmol) and NaH (60% dispersion in mineral oil, 136.8 mg, 4.094 mmol) in distilled DMF (10 mL) with 3-bromo-1-propanol (621 mg, 4.094 mmol) ), as described above, gave compound 14 (480.7 mg, 1.992 mmol, 73 %) as dark navy oil.: Rf = 0.33 (n-hexane/EtOAc = 1:1); IR (neat, cm-1) 3365, 3065, 2947, 1592, 1487, 1380, 1272, 1130, 1044; 1H NMR (400 MHz, CD3OD) delta 6.72~6.76 (m, 2H), 6.51~6.61 (m, 6H), 3.66 (t, 2H, J = 5.6 Hz), 3.60 (t, 2H, J = 7.6 Hz), 1.80 (m, 2H); 13C NMR (100 MHz, CD3OD) delta 145.0, 133.4, 123.7, 120.6, 115.0, 111.6, 59.2, 40.5, 27.7; MS (FAB) m/z 241.1 (M+).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 513 - 517

17
[ 135-67-1 ]
[ 1361227-58-8 ]
[ 1428932-80-2 ]

Yield	Reaction Conditions	Operation in experiment
77%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 110℃; for 1h;	[0094] In a 500 ml flask, 320 ml of toluene were degassed during 2 hours. 3-Bromo SBF (9.9 g, 0.025 mol), sodium tert. butylate (tBuONa, 4.92 g, 0.05 mol) and phenoxazine (4,6g, 0.025 mol) were added and after 30 min, a mixture of Bis-dibenzylideneacetone palladium (Pd(dba)2) and Tris-tert.-butylphosphine (P(tBu)3) previously prepared was slowly added. [0095] The solution was warmed to 110 C for one hour and then filtrated on a celite pad. After evaporation of the solvent, the solid recovered was recrystallised in ethanol to afford 9.4 g of a white solid (77 % yield).

Reference： [1]Patent: EP2574608,2013,A1 .Location in patent: Paragraph 0092; 0093; 0094; 0095

18
[ 135-67-1 ]
[ 30363-03-2 ]
2,4,6-tri(4-(10H-phenoxazin-10H-yl)phenyl)-1,3,5-triazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96.5%		(2) Synthesis of Compound 3 To a two-neck flask having been substituted with nitrogen, 2,4,6-tri(4-bromophenyl)-1,3,5-triazine (2.0 mmol, 1.09 g), phenoxazine (6. 6 mmol, 1.22g), potassium carbonate (19.8 mmol, 2.74 g) and 60 mL of toluene were added, and stirred under room temperature for 10 minutes. A mixed solution of palladium(II) acetate (0.20 mmol, 45.0 mg), tri-tert-butylphosphine (0.73 mmol, 147.7 mg) and 60 mL of toluene was added thereto, and the mixture was heated under refluxing for 24 hours. After standing to cool to room temperature, chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off. 2,4,6-tri(4-N-Phenoxazylphenyl)-1,3,5-triazine as the target product was isolated and purified by silica gel chromatography with a mixed solvent of chloroform and hexane (1/1) (yield amount: 1.65 g, yield: 96.5%). 1H-NMR (CDCl3, 300 MHz) delta = 6.06 (d, 6H), 6.63 (t, 6H), 6.69 (t, 6H), 6.73 (d, 6H), 7.60 (d, 6H), 9.01 (d, 6H) MS MALDI-MS m/z: 852

Reference： [1]Chemistry of Materials,2013,vol. 25,p. 3766 - 3771
[2]Patent: EP2808323,2014,A1 .Location in patent: Paragraph 0098-0099

19
[ 109-65-9 ]
[ 135-67-1 ]
10-butyl-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium hydroxide In dimethyl sulfoxide at 20℃; for 24h;	2.4.1 10-Butyl-10H-phenoxazine (1) To a phenoxazine (1.5g, 0.0082mol) solution in dry DMSO (22.5mL), sodium hydroxide (2.76g, 0.069mol) and 1-bromobutane (1.89g, 0.0137mol) were slowly added at room temperature and stirred for 24h. Then the reaction mixture was poured into water and extracted with ethyl acetate. The organic phase was separated and dried over anhydrous MgSO4. After removing the solvent, the residue was purified by column chromatography using ethyl acetate-hexane (1:10; v/v) as the eluent to give 1, colorless viscous liquid (1.8g, 92%). 1H NMR (500MHz, d6-DMSO): δ=6.81 (d, J=8.7Hz, 2H), 6.63-6.67 (m, 4H), 3.53 (t, J=7.7Hz, 2H), 1.50-1.54 (m, 2H), 1.38-1.43 (m, 2H), 0.94ppm (t, J=7.3Hz, 3H).
91%	With sodium hydroxide In dimethyl sulfoxide at 20℃; for 24h;	10-Butyl-10H-phenoxazine (1) Sodium hydroxide (7.36 g, 0.184 mol) and 1-bromobutane (6.62 g, 0.048 mol) were slowly added to a phenoxazine (4.0 g, 0.022 mol) solution in dry DMSO (50 mL) at room temperature and stirred for 24 h. Then, the reaction mixture was poured into water and extracted with ethyl acetate. The organic phase was separated and dried over anhydrous MgSO4. After removing the solvent, the residue was purified by column chromatography using ethyl acetate-hexane (1:10; v/v) as the eluent to give 1, colorless viscous liquid (4.78 g, 91%). 1H NMR (500 MHz, d6-DMSO): δ = 6.81 (d, J = 8.7 Hz, 2H), 6.63-6.67 (m, 4H), 3.53 (t, J = 7.7 Hz, 2H), 1.50-1.54 (m, 2H), 1.38-1.43 (m, 2H), 0.94 ppm (t, J = 7.3 Hz, 3H).
82%	With potassium hydroxide In dimethyl sulfoxide at 20℃; for 12h; Inert atmosphere;

80%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 25℃; for 3.5h; Inert atmosphere; Cooling with ice;
60%	With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere;
	With potassium <i>tert</i>-butylate In tetrahydrofuran Inert atmosphere;

Reference： [1]Lee, Woosung; Yuk, Sim Bum; Choi, Jun; Kim, Hae Jung; Kim, Hyun Woo; Kim, Se Hun; Kim, Boeun; Ko, Min Jae; Kim, Jae Pil [Dyes and Pigments, 2014, vol. 102, p. 13 - 21]
[2]Lee, Woosung; Choi, Jun; Namgoong, Jin Woong; Kim, Se Hun; Sun, Kyung Chul; Jeong, Sung Hoon; Yoo, Kicheon; Ko, Min Jae; Kim, Jae Pil [Dyes and Pigments, 2014, vol. 104, p. 185 - 193]
[3]Shen, Chao; Wang, Xingzhu; Tang, Shasha; Courté, Marc; Fichou, Denis [ChemPhysChem, 2017, vol. 18, # 10, p. 1302 - 1307]
[4]Zhang, Fang; Liang, Xiaozhong; Li, Da; Yin, Xiangkai; Tian, Xia; Li, Bin; Xu, Hong; Guo, Kunpeng; Li, Jie [Journal of Materials Chemistry C, 2019, vol. 7, # 39, p. 12328 - 12335]
[5]Dick, Bernhard; Dong, Yu; Elmali, Ayhan; Karatay, Ahmet; Zhao, Jianzhang [ChemPhysChem, 2020]
[6]Wu, Yuezhen; Zhang, Quande; Li, Jie; Tian, Xia; Li, Da; Lu, Xiaoqing; Xu, Bingshe; Wu, Yucheng; Guo, Kunpeng [Journal of Materials Chemistry C, 2019, vol. 7, # 7, p. 1974 - 1981]

20
[ 135-67-1 ]
[ 589-87-7 ]
[ 71041-21-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	With copper(l) iodide; rac-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane; at 101℃; for 6h;Inert atmosphere;	phenoxazine (10g, 54.5mmol),4-bromoiodobenzene (17 g, 60 mmol), 1,2-cyclohexanediamine (0.63 g,5.5 mmol), sodium tert-butoxide (10.5 g, 109 mmol) and cuprous iodide (0.21 g, 1.1 mmol) were placed in a 250 mL single-necked flask.Under the protection of nitrogen,Add anhydrous 1,4-dioxane (100 mL),Stir at 101 C for 6 hours under reflux.The reaction system is cooled to room temperature, and the dichloromethane is separated and separated.The organic layer was dried with anhydrous magnesiumColumn chromatography (eluent is a 1:4 mixture of dichloromethane and petroleum ether),Obtaining compound a2 10-(4-bromophenyl)-phenoxazine 15g,The yield was 81%.
81%	With copper(l) iodide; rac-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane; for 6h;Inert atmosphere; Reflux;	100 mL of 1,4-dioxane was placed in a flask having been substituted with nitrogen, to which 10H-phenoxazine (10 g, 54.5 mmol), 1-bromo-4-iodobenzene (17 g, 60 mmol), copper iodide (0.21 g, 1.09 mmol), sodium tert-butoxide (10.5 g, 109 mmol), and 1,2-diaminocyclohexane (0.62 g, 5.45 mmol) were then added. The reaction solution was heated and refluxed for 6 hours. Thereafter, the temperature was lowered, and impurities were removed with Celite. The resulting filtrate was purified by column chromatography to provide an intermediate (4) as a white solid matter (15 g, 81%). 1H NMR (500 MHz, CDCl3): 7.72 (d, J=9 Hz, 2H), 7.23 (d, J=8.5 Hz, 2H), 6.74-6.57 (m, 6H), 5.91 (dd, J=9 Hz, 1.5 Hz, 2H)
75%		(1) phenoxazine (1.66 g, 5.00 mmol),Sodium tert-butoxide (0.96g, 10.00mmol) is dissolved in 80mL of 1,4-dioxane,Stir at room temperature for 30 min under a nitrogen atmosphere. CuI (0.10 g, 0.50 mmol) was then added,1,10-phenanthroline (0.10 g, 0.50 mmol), p-bromoiodobenzene (1.69 g, 6.00 mmol) was reacted at 110 C for 24 h. Product 1 was obtained as a white solid with a yield of 75%. The reaction formula is as follows:

72%	With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 190℃; for 2h;Inert atmosphere;	Put 0.80g (1.0eq, 4.4mmol) of 10H-benzoxazine, 1.6g (1.3eq, 5.7mmol) of 4-bromoiodobenzene, and 0.090g (0.080eq, 0.35mmol) of 18-crown-6 , 0.14 g (0.52 eq, 2.3 mmol) of copper (powder) and 2.4 g (4.0 eq, 17 mmol) of potassium carbonate were added to the reaction vessel and vacuum dried, and the reaction vessel was filled with nitrogen. 11 mL of 1,2-dichlorobenzene was added to the reaction vessel, and the mixture was refluxed and stirred at a temperature of 190C for 2 hours. After the reaction was completed, the organic layer was extracted therefrom by using distilled water and ethyl acetate. The extracted organic layer was dried by using anhydrous magnesium sulfate, and filtered through Celite, and the solvent was evaporated therefrom. Then, column chromatography was performed on it to obtain 1.1 g (72% yield) of Intermediate 15(1) (ie 10-(4-bromophenyl)-10H-benzoxazine).
70%		Phenoxazine (1.83 g, 10 mmol), p-bromoiodobenzene (3.1 g, 11 mmol),Cuprous iodide (0.38 g, 0.2 mmol) and sodium tert-butoxide (1.92 g, 20 mmol)Add to the reaction flask and exchange nitrogen three times (10 min/time).Injecting solvent (1,4-dioxane) under nitrogen protection,After the raw material is partially dissolved, 2 ml of 1,2-diaminocyclohexane (coordinating agent) is injected.After the injection, the reaction was refluxed at 110 C for 6 h, extracted, concentrated, and powdered.Purification by column chromatography gave a white solid product 2, yield 70%.
67%	With copper(l) iodide; sodium t-butanolate; In 1,4-dioxane; at 110℃; for 6h;Inert atmosphere;	(1) Under a nitrogen atmosphere, phenoxazine (V-a, 1.83 g, 10 mmol), p-Bromoiodobenzene (3.39 g, 12 mmol), Cuprous iodide (0.04 g, 0.22 mmol), Sodium tert-butoxide (2.11 g, 22 mmol) And cyclohexanediamine (0.13 g, 1.1 mmol), Dissolved in ultra dry 1,4-dioxane (30ml), The system was heated to 110 C and refluxed for 6 hours. After the system is cooled, it is extracted with deionized water and dichloromethane. The obtained organic phase was dried over anhydrous MgSO 4 and dried. Concentrated under reduced pressure, Separation and purification by column chromatography, The stationary phase is 300-400 mesh silica gel. The mobile phase is dichloromethane/petroleum ether (1:9 by volume), Finally, the white solid intermediate product VI-a 2.27g was obtained. The yield was 67%.
65.8%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; at 80℃; for 20h;	4.0 g (21.84 mmol) of phenoxazine were weighed,2.78 ml (6.12 g, 21.84 mmol) of bromoiodobenzene,14.24 g (43.7 mmol) of anhydrous cesium carbonate,1.64 ml (0.66 mmol) of tri-tert-butylphosphine,0.1 g (0.44 mmol) of palladium acetate in a 250 mL three-necked flask,Then, 100 mL of anhydrous toluene was added as a reaction solvent.After removing the air,And the mixture was heated to 80 C for 20 hours.After completion of the reaction,After the solvent was removed under reduced pressure, the reaction solution was extracted with methylene chloride (100 mL x 3)The extracts were combined and dried over anhydrous magnesium sulphate, Spin-drying the solvent, and drying. The crude product was purified by column chromatography using petroleum ether and dichloromethane (PE: DCM = 15: 1) as eluant to give 4.85 g of a white crystalline powder in 65.8% yield.
65.7%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In tetrahydrofuran; at 100℃; for 20h;Inert atmosphere;	Weigh 2.0g (10.92mmol) phenoxazine, 3.08g (10.92mmol) p-bromoiodobenzene, 7.12g (21.85mmol) of anhydrous cesium carbonate, 0.82ml (0.33mmol) of tri-tert-butylphosphine, 0.049 g (0.22 mmol) of palladium acetate in 250 mL three neck bottles, and then 80 mL of dry tetrahydrofuran was added as the reaction solvent. Under nitrogen, and heated to 100 C for 20 hours. After the reaction, The reaction solution was extracted with dichloromethane (50 mL x 3) after solvent extraction, The extracts were combined and dried over anhydrous magnesium sulfate, Spin dry solvent, dry. The crude product was purified by column chromatography using petroleum ether and dichloromethane (PE:DCM=15:1) as eluent to give 2.42 g of white crystalline powder, Yield 65.7%.
65%	With copper(l) iodide; rac-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane; at 110℃; for 6h;Inert atmosphere;	Add phenoxazine (1equiv.), 2-bromo-5-iodobenzene (1equiv.), cuprous iodide (0.02equiv.) and sodium tert-butoxide (2equiv.) into the reaction tube, nitrogen was pumped three times, 50 mL of 1,4-dioxane was added under the protection of nitrogen, and 1,2-diaminocyclohexane (complexing agent) was added after the raw materials were dissolved. The reaction was stirred at 110C for 6h. After cooling to room temperature, 100 mL of water was added to the reaction mixture and extracted with dichloromethane to obtain an organic layer. Finally, the organic layer was concentrated to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a white solid product O-Br with a yield of 65%.
41%	With copper(l) iodide; (S,S)-1,2-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane; at 90℃; for 48h;Inert atmosphere;	phenoxazine (3.66g, 19.98mmol, 1.0 equivalent), 1-bromo-4-iodobenzene (6.22g, 21.97mmol, 1.1 equivalent), cuprous iodide (76.1mg, 0.40mmol) , 0.02 equivalent) and sodium tert-butoxide (3.84g, 39.95mmol, 2.0 equivalent) were added to a dry three-necked flask equipped with magnetic stirring.Pump nitrogen for three times, then add 1,2-trans-cyclohexanediamine (0.25mL, 2.00mmol, 0.1 equivalent) and 1,4-dioxane (80mL) under nitrogen protection, and place the mixture in an oil bath And stir the reaction at 90C.It was monitored by thin layer chromatography until the reaction was completed, and the reaction was stopped after 48 hours.The resulting mixture was cooled to room temperature and quenched by adding water.The mixture was extracted three times with dichloromethane.The combined organic layer was washed with water, dried over anhydrous sodium sulfate and filtered.The filtrate was concentrated under reduced pressure, and the sample was purified by silica gel column chromatography (eluent: petroleum ether) to obtain 2.77 g of a white solid with a yield of 41%.
37%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In 5,5-dimethyl-1,3-cyclohexadiene; at 105 - 115℃; for 1h;Inert atmosphere;	First, under an argon gas flow, phenoxazine (71.8 g, 360 mmol) and 1-bromo-4-iodobenzene (102 g, 360 mmol) and xylene (1.1 liters) was added to 3 liter flask. The internal temperature was raised to 105 C.,After adding tBu3P· HBF4 (4.18 g, 14.4 mmol) and Pd2(dba 3) (6.59 g, 7.20 mmol)tBuONa (41.6 g, 433 mmol) was added in portions. Thereafter, the temperature was raised to 115 C. and stirred for 1 hour. After cooling to room temperature, the reaction solution was added to water (1.8 liter), and the organic layer was separated. The organic layer was washed with water (500 ml), separated, and concentrated under reduced pressure. The obtained crude product (107 g) was purified by silica gel column chromatography (2 kg, development: toluene / heptane = 1/2) to obtain the desired product (yield 47 g, yield 37%).
29.2%	With copper(l) iodide; rac-diaminocyclohexane; sodium t-butanolate; In 1,4-dioxane;Reflux;	20.0 g (109 mmol) of 10H-phenoxazine in a 1-neck 1L flask,1-bromo-4-iodobenzene (1-bromo-4-iodobenzene) 37.1 g (131 mmol),CuI 0.45 g (2.2 mmol),1,2-diaminocyclohexane (1,2-diaminocyclohexane) 1.2 g (10.9 mmol),21.0 g (218 mmol) of NaOtBu and 545 mL of Dioxane were mixed and refluxed.After completion of the reaction, after cooling to room temperature, distilled water and DCM were added and extracted. The separated organic layer was dried over anhydrous Na2SO4, and the solvent was removed under reduced pressure. The reaction product was purified by silica gel column chromatography (Hex:DCM) to obtain 10.8 g (yield: 29.2%) of the compound (intermediate (5)) as a white solid.
28%	With copper; potassium carbonate; In N,N-dimethyl-formamide; at 130℃; for 16h;Inert atmosphere;	Phenoxazine (5.0 g, 2.73 mmol), 1-bromo-4-iodobenzene (11.6 g, 41.0 mmol), potassium carbonate (15.1 g, 109.2 mmol) and copper powder (3.5 g, 54.6 mmol) were added to DMF (100 mL) under N2. The solution was stirred at 130 C for 16h. After cooling to room temperature, the solvent was removed under reduced pressure. Purification by column chromatography (SiO2, hexanes/CH2Cl2 10:1) afforded the CP6 (2.57 g, 28% yield) as a white solid.
25%	With copper; potassium carbonate; at 170℃; for 7h;	Potassium carbonate (7.8 g, 60 mmol), copper powder (0.5 g, 8 mmol), 4-iodo-bromobenzene (12.4 g, 44 mmol), and phenoxazine (8 g, 40 mmol) were added to a 100 mL one-port round-bottomed flask. The mixture was heated to 170 C for 7 h. The reaction mixture was cooled to 130 C and ethyl acetate was added. The resulting mixture was stirred for 30 min at 130 C and then filtered. The filtrate was evaporated to remove the solvent. The crude product was purified by column chromatography on silica gel using petroleum ether as eluent to afford white solid (3.6 g, 25%). 1H NMR (CDCl3, 400 MHz), (TMS, ppm):7.59 (d, 2H), 7.13-6.98 (m, 6H), 6.82-6.75 (m, 4H). GC-MS: m/z = 337.3.
	With copper(l) iodide; potassium carbonate; In water; at 140℃; for 12h;Inert atmosphere;	A, will 1mmol phenoxazin, 1mmol the bromine monoiodo-benzene, 0.02mmol cuprous iodide, 1mmol potassium carbonate in water after baking in addition to 50 ml three-necked round bottom flask, under the protection of argon gas 140 C stirring under 12h, stop heating reaction recovery room temperature the reaction mixture is washed with water three times, then dichloromethane is used for extraction, the organic layer with anhydrous NaSO4drying, pressure reducing the spin vaporization of go out the solvent, the product column chromatography purification to obtain 10 - (4-bromophenyl) - 10 hydrogen-phenoxazin.
	With copper(l) iodide; potassium carbonate; In toluene; at 80℃; for 6h;	Compound F33 can be synthesized by a person of ordinary skill following Scheme 11 illustrated in FIG. 12. In the first step, compound S11-1 (available for purchase from Acros Organics, CAS No. 589-87-7) is combined with compound S11-2 (available for purchase from Acros Organics, CAS No. 135-67-1), K2CO3 and Cul in toluene at 80 C to form compound S11-3. In the second step, compound SI 1-3 is combined with compound S11-4 (available for purchase from Acros Organics, CAS 1692-15-5), Pd(OAc)2 and K3P04 in THF at 45 C for 24 hours to form compound F33. It is understood that steps 1 and 2 can be performed and optimized by a person having ordinary skill in the art without undue experimentation.
	With copper; potassium carbonate; In N,N-dimethyl-formamide; at 130℃; for 24h;Inert atmosphere;	2-bromo-5-iodo1,3-dimethylxylene (10 mmol), phenoxazine (10 mmol), Cu (20 mmol), under a nitrogen atmosphereK2CO3 (20 mmol) and N,N-dimethylformamide (20 ml) were combined to form a solution.The above mixed solution was evacuated three times with nitrogen, and heated and stirred at 130 C for 24 h. The reaction mixture was filtered through celite and usedWash with dichloromethane (20 ml).The solvent was evaporated under reduced pressure and then purified by column chromatography (hexane / dichloromethane (10:1))A white solid 10-(4-bromophenyl)-phenoxazine S5-2 was obtained.

Reference： [1]Journal of Materials Chemistry C,2015,vol. 3,p. 9122 - 9130
[2]Patent: CN108148055,2018,A .Location in patent: Paragraph 0122; 0126; 0127
[3]Patent: US2019/345095,2019,A1 .Location in patent: Paragraph 0222-0224
[4]Patent: CN110724128,2020,A .Location in patent: Paragraph 0050-0054
[5]Patent: CN111333615,2020,A .Location in patent: Paragraph 060-0610
[6]Patent: CN109593079,2019,A .Location in patent: Paragraph 0091; 0095; 0096; 0097
[7]Journal of Materials Chemistry C,2019,vol. 7,p. 11953 - 11963
[8]Patent: CN109134396,2019,A .Location in patent: Paragraph 0066-0068
[9]Patent: CN106243086,2016,A .Location in patent: Paragraph 0013
[10]Patent: CN106243091,2016,A .Location in patent: Paragraph 0022
[11]Patent: CN113429402,2021,A .Location in patent: Paragraph 0025-0028
[12]Chemistry of Materials,2016,vol. 28,p. 5667 - 5679
[13]Chemistry - An Asian Journal,2017,vol. 12,p. 2494 - 2500
[14]Patent: CN111471043,2020,A .Location in patent: Paragraph 0072-0074
[15]Patent: JP2018/111672,2018,A .Location in patent: Paragraph 0194; 0199; 0201-0202
[16]Patent: KR102279134,2021,B1 .Location in patent: Paragraph 0157-0159
[17]Bioorganic Chemistry,2018,vol. 81,p. 504 - 511
[18]Dyes and Pigments,2014,vol. 101,p. 67 - 73
[19]Advanced Functional Materials,2016,vol. 26,p. 1813 - 1821
[20]Organic electronics,2016,vol. 34,p. 208 - 217
[21]Patent: CN105924472,2016,A .Location in patent: Paragraph 0074; 0075
[22]Patent: CN106661001,2017,A .Location in patent: Paragraph 0360; 0361; 0365; 0377
[23]Patent: CN109134520,2019,A .Location in patent: Paragraph 0086; 0087

21
[ 135-67-1 ]
[ 864377-31-1 ]
C₃₃H₂₂N₄O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.3%		(2) Synthesis of Compound 4 To a two-neck flask having been substituted with nitrogen, <strong>[864377-31-1]2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine</strong> (3.50 mmol, 1.36g), phenoxazine (3. 85 mmol, 713.1 mg), potassium carbonate (11.6 mmol, 1.60 g) and 20 mL of toluene were added, and stirred under room temperature for 10 minutes. A mixed solution of palladium(II) acetate (0.12 mmol, 27.0 mg), tri-tert-butylphosphine (0.42 mmol, 85.0 mg) and 20 mL of toluene was added thereto, and the mixture was heated under refluxing for 24 hours. After standing to cool to room temperature, chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off. The compound 4 was isolated and purified by silica gel chromatography with a mixed solvent of chloroform and hexane (1/1) (yield amount: 1.45 g, yield: 84.3%). 1H-NMR (CDCl3, 300 MHz) delta = 5.99 (d, 2H), 6.61 (t, 2H), 6.67 (t, 2H), 6.73 (d, 2H), 7.55 (m, 7H), 7.82 (t, 1H), 8.75 (s, 1H), 8.76 (d, 4H), 8.90 (d, 1H) MS MALDI-MS m/z: 490

Reference： [1]Patent: EP2808323,2014,A1 .Location in patent: Paragraph 0102-0103
[2]Patent: KR2017/101586,2017,A .Location in patent: Paragraph 0168

22
[ 135-67-1 ]
[ 890148-78-4 ]
2,4,6-tri(3-N-phenoxazylphenyl)-1,3,5-triazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95.3%		(2) Synthesis of Compound 6 To a two-neck flask having been substituted with nitrogen, <strong>[890148-78-4]2,4,6-tri(3-bromophenyl)-1,3,5-triazine</strong> (2.00 mmol, 1.09 g), phenoxazine (6.60 mmol, 1.22 g), potassium carbonate (19.8 mmol, 2.74 g) and 60 mL of toluene were added, and stirred under room temperature for 10 minutes. A mixed solution of palladium(II) acetate (0.20 mmol, 45.0 mg), tri-tert-butylphosphine (0.73 mmol, 147.7 mg) and 60 mL of toluene was added thereto, and the mixture was heated under refluxing for 24 hours. After standing to cool to room temperature, chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off under heating and reduced pressure. The resulting solid matter was washed with chloroform, thereby providing 2,4,6-tri(3-N-phenoxazylphenyl)-1,3,5-triazine as the target product (yield amount: 1.63 g, yield: 95.3%). 1H-NMR (CDCl3, 300 MHz) delta = 5.91 (d, 6H), 6.52 (t, 6H), 6.63 (t, 6H), 6.68 (d, 6H), 7.57 (d, 3H), 7.78 (t, 3H), 8.75 (s, 3H), 8.85 (d, 3H) MS MALDI-MS m/z: 852

Reference： [1]Patent: EP2808323,2014,A1 .Location in patent: Paragraph 0110-0111

23
[ 135-67-1 ]
[ 98-54-4 ]
4-(tert-butyl)-2-(10H-phenoxazin-10-yl)phenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With oxygen; potassium carbonate; 10H-phenotellurazine In 1,2-dichloro-benzene at 130℃; for 3h; Sealed tube;
87%	With oxygen; potassium carbonate In 1,2-dichloro-benzene at 130℃; for 2h;	1. Typical procedure for the synthesis of 3a General procedure: A stirred mixture of phenothiazine (100 mg, 0.5 mmol),3,5-dimethylphenol (183 mg, 1.5 mmol), and K2CO3 (69 mg,0.5 mmol) in ODCB (1.5 mL) was heated to 130 oC for 6 h under O2 balloon atmosphere. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/EtOAc, 20:1) para-3a (103 mg, 64%) and ortho-3a (34 mg, 21%) were obtained as white solids. Other compounds were synthesized similarly, and the spectroscopic data of 3a-3m and the sulfoxide of 3g are as follows.
69%	With oxygen; potassium carbonate In 1,2-dichloro-benzene at 130℃; for 3h; Sealed tube;

66%	With (1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluorophthalocyaninato)iron(II); N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 3h;
64%	With oxygen In acetic acid at 130℃; for 24h; Sealed tube;

Reference： [1]Cremer, Christopher; Goswami, Monalisa; Rank, Christian K.; de Bruin, Bas; Patureau, Frederic W. [Angewandte Chemie - International Edition, 2021, vol. 60, # 12, p. 6451 - 6456][Angew. Chem., 2021, vol. 133, # 12, p. 6525 - 6530,6]
[2]Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Bulletin of the Korean Chemical Society, 2015, vol. 36, # 11, p. 2765 - 2768]
[3]Benchouaia, Rajaa; Nandi, Shiny; Maurer, Clemens; Patureau, Frederic W. [Journal of Organic Chemistry, 2022, vol. 87, # 7, p. 4926 - 4935]
[4]Purtsas, Alexander; Rosenkranz, Marco; Dmitrieva, Evgenia; Kataeva, Olga; Knölker, Hans-Joachim [Chemistry - A European Journal, 2022, vol. 28, # 21]
[5]Louillat-Habermeyer, Marie-Laure; Jin, Rongwei; Patureau, Frederic W. [Angewandte Chemie - International Edition, 2015, vol. 54, # 13, p. 4102 - 4104][Angew. Chem., 2015, vol. 127, # 13, p. 2]

24
[ 135-67-1 ]
[ 3164-13-4 ]
10-[4-(benzo[d]oxazol-2-yl)phenyl]-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
> 65%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; for 15h;Reflux;	To a solution of <strong>[3164-13-4]2-(4-bromophenyl)benzo[d]oxazole</strong> (740 mg, 2.70 mmol), phenoxazine (495mg, 2.70 mmol) and potassium carbonate (1.11 g, 8.00 mmol) in toluene (10 mL), a solution of palladium(II) acetate (191 mg, 0.85 mmol) and tri-tert-butylphosphine (202 mg, 1.00 mmol) in toluene (5 mL) was added, with stirring. The mixture was stirred and heated under reflux for 15h. The cooled mixture was partitioned between ethyl acetate and water. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (eluent: chloroform/hexane = 1/1 (v/v)) afforded 661 mg of BOX. The yield was over 65%. The compound was further purified by sublimation under reduced pressure for OLED fabrication.
65%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; at 100℃; for 15h;Inert atmosphere;	(0136) To a 100 ml two-neck flask having been substituted with nitrogen, phenoxazine (2.7 mmol, 0.50 g), 2-(4-bromophenyl)benzothiazol (2.7 mmol, 0.73 g) were poured. To the mixture, 10 mL of dry dehydrated toluene, potassium carbonate (8.0 mmol, 1.1 g), palladium acetate (0.85 mmol, 0.18 g), tri-tert-butylphosphine (1.0 mmol, 0.22 g) were added. The mixture was stirred in a nitrogen atmosphere at 100 C. for fifteen hours. After stirring the mixture, 200 ml of ethyl acetate and saturated saline were added to the mixture, and an organic layer and a water layer were separated. The organic layer was dehydrated over magnesium sulfate. After the dehydration, and the mixture was filtered off under suction to provide a filtrate. The obtained filtrate was dissolved in chloroform and then refined by silica gel column chromatography (developing solvent: chloroform/hexane=1/1 (v/v)). After the refining, the obtained fraction was condensed to collect a solid matter, and a yellow powder-like solid matter was obtained (yield amount: 0.65 g, yield: 65%). FIG. 3 shows 1H-NMR (CDCl3, 500 MHz).

Reference： [1]Chemistry Letters,2015,vol. 44,p. 360 - 362
[2]Patent: US2015/239880,2015,A1 .Location in patent: Paragraph 0136

25
[ 135-67-1 ]
[ 19654-19-4 ]
10-[4-(benzo[d]thiazol-2-yl)phenyl]-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene for 15h; Reflux;	Synthetic procedure and characterization data for10-(4-(benzo[d]thiazol-2-yl)phenyl)-10H-phenoxazine (BT) To a solution of 2-(4-bromophenyl)benzo[d]thiazole (725 mg, 2.50 mmol), phenoxazine (696mg, 3.80 mmol) and potassium carbonate (995 mg, 7.20 mmol) in toluene (10 mL), a solution of palladium(II) acetate (56.1 mg, 0.25 mmol) and tri-tert-butylphosphine (50.6 mg, 0.25 mmol) in toluene (5 mL) was added, with stirring. The mixture was stirred and heated under reflux for 15h. The cooled mixture was partitioned between ethyl acetate and water. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, and concentrated in vacuo. Purification of the residue by column chromatography (eluent: chloroform/hexane = 1/3 (v/v)) afforded 765 mg of BT. The yield was over 78%. The compound was further purified by sublimation under reduced pressure for organic light-emitting diode (OLED) fabrication.
78%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene at 100℃; for 15h; Inert atmosphere;	1 Synthesis of Compound 1 To a 100 ml two-neck flask having been substituted with nitrogen, phenoxazine (3.8 mmol, 0.70 g), 2-(4-bromophenyl)benzothiazol (2.5 mmol, 0.74 g) were poured. To the mixture, 10 mL of dry dehydrated toluene, potassium carbonate (7.2 mmol, 1.0 g), palladium acetate (0.25 mmol, 0.060 g), tri-tert-butylphosphine (0.25 mmol, 0.051 g) were added. The mixture was stirred in a nitrogen atmosphere at 100°C. for 15 hours. After stirring the mixture, 200 ml of ethyl acetate and saturated saline were added to the mixture, and an organic layer and a water layer were separated. The organic layer was dehydrated over magnesium sulfate. After the dehydration, and the mixture was filtered off under suction to provide a filtrate. The obtained filtrate was dissolved in chloroform and refined by silica gel column chromatography (developing solvent: chloroform/hexane=1/3 (v/v)). After the refining, the obtained fraction was condensed to collect a solid matter, and a yellow powder-like solid matter was obtained (yield amount: 0.78 g, yield: 78%). FIG. 2 shows 1H-NMR (CDCl3, 500 MHz).

Reference： [1]Sagara, Yuta; Shizu, Katsuyuki; Tanaka, Hiroyuki; Miyazaki, Hiroshi; Goushi, Kenichi; Kaji, Hironori; Adachi, Chihaya [Chemistry Letters, 2015, vol. 44, # 3, p. 360 - 362]
[2]Current Patent Assignee: KYUSHU UNIVERSITY - US2015/239880, 2015, A1 Location in patent: Paragraph 0133; 0134

26
[ 948-65-2 ]
[ 135-67-1 ]
10-(2-phenyl-1H-indol-3-yl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium peroxodisulfate In acetonitrile at 20℃; for 4h; regioselective reaction;
93%	With oxygen; potassium carbonate In 1,2-dichloro-benzene at 130℃; for 3h;	1. Typical procedure for the synthesis of 3a General procedure: A stirred mixture of phenothiazine (100 mg, 0.5 mmol),3,5-dimethylphenol (183 mg, 1.5 mmol), and K2CO3 (69 mg,0.5 mmol) in ODCB (1.5 mL) was heated to 130 oC for 6 h under O2 balloon atmosphere. After the usual aqueous extractive workup and column chromatographic purification process (hexanes/EtOAc, 20:1) para-3a (103 mg, 64%) and ortho-3a (34 mg, 21%) were obtained as white solids. Other compounds were synthesized similarly, and the spectroscopic data of 3a-3m and the sulfoxide of 3g are as follows.
87%	With oxygen; potassium carbonate In 1,2-dichloro-benzene at 130℃; for 3h; Sealed tube;

61%

With oxygen; NaNO₂ In toluene at 0 - 20℃; Sealed tube;

Reference： [1]Lei, Aiwen; Wang, Pengjie; Wang, Shengchun; Wang, Xiaoyu; Yi, Hong; Zhang, He; Zhang, Heng [Green Chemistry, 2022, vol. 24, # 1, p. 147 - 151]
[2]Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Bulletin of the Korean Chemical Society, 2015, vol. 36, # 11, p. 2765 - 2768]
[3]Benchouaia, Rajaa; Nandi, Shiny; Maurer, Clemens; Patureau, Frederic W. [Journal of Organic Chemistry, 2022, vol. 87, # 7, p. 4926 - 4935]
[4]Bering, Luis; D'Ottavio, Laura; Sirvinskaite, Giedre; Antonchick, Andrey P. [Chemical Communications, 2018, vol. 54, # 92, p. 13022 - 13025]

27
[ 689260-53-5 ]
[ 135-67-1 ]
C₃₈H₃₈BNO [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2015,vol. 54,p. 15231 - 15235
Angew. Chem.,2015,vol. 127,p. 15446 - 15450,5

28
[ 689260-53-5 ]
[ 135-67-1 ]
10-(4-bromo-3,5-dimethylphenyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper; potassium carbonate; In N,N-dimethyl-formamide; at 130℃; for 24h;Inert atmosphere;	2-bromo-5-iodo1,3-dimethylbenzene (10 mmol), phenoxazine (10 mmol), Cu (20 mmol), under a nitrogen atmosphereK2CO3 (20 mmol) and N,N-dimethylformamide (20 ml) were combined to form a solution.The above mixed solution was evacuated three times with nitrogen, and heated and stirred at 130 C for 24 h. The reaction mixture was filtered through celite and usedWash with dichloromethane (20 ml).The solvent was evaporated under reduced pressure and purified by column chromatography (hexane/dichloromethane: 10:1) to yield 10-(4-bromo-3,5-dimethylphenyl)-phenoxazine S5- 1.

Reference： [1]Angewandte Chemie - International Edition,2015,vol. 54,p. 15231 - 15235
Angew. Chem.,2015,vol. 127,p. 15446 - 15450,5
[2]Patent: CN109134520,2019,A .Location in patent: Paragraph 0084; 0085

29
[ 135-67-1 ]
[ 383-29-9 ]
C₃₆H₂₄N₂O₄S [ No CAS ]

Reference： [1]Journal of Materials Chemistry C,2016,vol. 4,p. 3705 - 3708

30
[ 135-67-1 ]
[ 14862-52-3 ]
10,10'-(5-chloro-1,3-phenylene)bis(10H-phenoxazine) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene for 4h; Reflux; Inert atmosphere;	13 Synthesis of intermediate M-13 In the round bottom flask was charged with 1,3-dibromo-5-chlorobenzene 25g (92.47mmol) and phenoxazine 33.9g (184.9mmol) into a sodium t- butoxide 26.7g (277.41mmol) was added to 463ml toluene dissolved. Here Pd (dba)2 0.266g (0.462mmol) and tri-tert-butylphosphine was put 0.187g (0.924mmol) in turn and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After the reaction the organic layer was then extracted with ethyl acetate dry distilled over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product n- hexane / dichloromethane (8: 2 by volume) to yield the silica gel column 36.9g (yield 84%) was purified by chromatography to give the target compound as an intermediate M-13 as a white solid.
76%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 80℃; for 4h; Inert atmosphere;	2 Synthesis of intermediate M2-10: Under nitrogen, 1,3-dibromo-5-chlorobenzene (2.00g, 7.41mmol) and phenoxazine (2.85g, 15.56mmol) were added to 100mL anhydrous toluene in sequence. t-BuONa (2.85g, 29.64mmol), Pd2(dba)3 (339mg, 0.37mmol), P(t-Bu)3HBF4 (457mg, 1.11mmol), after deoxygenation for 10min, warmed to 80 , the reaction 4h, It becomes brownish black solution. After the reaction is completed, cool and filter with suction, collect the filtrate, add water and extract with DCM, collect the organic phase and dry with anhydrous Na2SO4, spin off the solvent, and purify by column chromatography (petroleum ether/DCM, 8/1, V/V), M2-10 white solid was obtained (2.68 g, 76%).
	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 80℃; for 4h; Inert atmosphere;	2.4. Synthesis of 9,9'-(5-chloro-1,3-phenylene)bis(9H-carbazole) General procedure: A mixture of 1,3-dibromo-5-chlorobenzene (2 g, 7.41 mmol), 9Hcarbazole(2.60 g, 15.56 mmol), tris(dibenzylideneacetone)dipalladium(339 mg, 0.37 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl (457 mg, 1.11 mmol) and sodium tert-butoxide (2.85 g,29.64 mmol) in 100 ml of toluene were heated at 80 °C for 4 h underargon. After cooling down to room temperature, the mixture was extractedwith dichloromethane. The combined organic extracts weredried over Na2SO4 and evaporated under reduced pressure. The crudeproduct was purified by column chromatography on silica gel usingpetroleum ether/dichloromethane (PE/DCM, 8/1, v/v) as the eluent toafford the target compound (2.46 g, 75%).

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR2016/8651, 2016, A Location in patent: Paragraph 0203-0205
[2]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN111170928, 2020, A Location in patent: Paragraph 0093-0098
[3]Ran, Quan; Zhang, Yuan-Lan; Hua, Xiaochen; Fung, Man-Keung; Liao, Liang-Sheng; Fan, Jian [Dyes and Pigments, 2019, vol. 162, p. 632 - 639]

31
[ 135-67-1 ]
[ 126759-30-6 ]
C₂₀H₁₄N₂O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With tributylphosphine; palladium diacetate; caesium carbonate; In toluene; for 8.0h;Inert atmosphere; Reflux;	<strong>[126759-30-6]3-bromo-4-nitrobenzoate methyl ester</strong> (20g, 76.9mmol), phenoxazine (14.1g, 76.9mmol), palladium acetate (0.8g, 3.8mmol), t-butyl phosphine (1.1g, 5.8mmol) and cesium carbonate (37.5g, 115.4mmol) were dissolved in toluene under nitrogen atmosphere and the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred and pentane was added, filtered, purified by silica gel column chromtography to obtain solid compound 29-a (15.6g, yield 56%).
56%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8.0h;Inert atmosphere; Reflux;	The <strong>[126759-30-6]3-bromo-4-nitro-benzoic acid methyl ester</strong> (20g, 76.9mmol), phenoxazine (14.1g, 76 . 9mmol), palladium acetate (0.8g, 3 . 8mmol), uncle butyl phosphine (1.1g, 5 . 8mmol) and cesium carbonate (37.5g, 115 . 4mmol) in dissolved in toluene, in the nitrogen atmosphere, heating reflux reaction 8 hours. Vacuum evaporation of the solvent, stirring pentane is added to the remaining substance, filtering, through a silica gel chromatography column to purify, to obtain solid compound 29-a (15.6g, yield 56%).

Reference： [1]Patent: CN105294670,2016,A .Location in patent: Paragraph 0144; 0146; 0147
[2]Patent: CN105481845,2016,A .Location in patent: Paragraph 0165; 0166

32
[ 135-67-1 ]
[ 6307-87-5 ]
C₂₀H₁₄N₂O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With tributylphosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;	<strong>[6307-87-5]3-bromo-5-nitrobenzoate methyl ester</strong> (20g, 76.9mmol), phenoxazine (14.1g, 76.9mmol), palladium acetate (0.8g, 3.8mmol), t-butyl phosphine (1.1g, 5.8mmol) and cesium carbonate (37.5g, 115.4mmol) were dissolved in toluene under nitrogen atmosphere and the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred and pentane was added, filtered, purified by silica gel column chromtography to obtain solid compound 40-a (14.5g, yield 52%).
52%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;	The <strong>[6307-87-5]3-bromo-5-nitro-benzoic acid methyl ester</strong> (20g, 76.9mmol), phenoxazine (14.1g, 76 . 9mmol), palladium acetate (0.8g, 3.8mmol), uncle butyl phosphine (1.1g, 5 . 8mmol) and cesium carbonate (37.5g, 115 . 4mmol) in dissolved in toluene, in the nitrogen atmosphere, heating reflux reaction 8 hours. Vacuum evaporation of the solvent, stirring pentane is added to the remaining substance, filtering, through a silica gel chromatography column to purify, to obtain solid compound 40-a (14.5g, yield 52%).

Reference： [1]Patent: CN105294670,2016,A .Location in patent: Paragraph 0177; 0178; 0179
[2]Patent: CN105481845,2016,A .Location in patent: Paragraph 0198; 0199

33
[ 38240-21-0 ]
[ 135-67-1 ]
[ 23351-91-9 ]
C₃₀H₁₇N₅OS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
21%		Except that 3-aminopyridine-2-thiol was used instead of 2-amino-4-hydroxypyridine, and 5-bromoisophthalate replaced by 2,2'-dibromo-4,4'-dicarboxy biphenyl, other synthesis process with Example 22. Purified by silica gel column chromatography to give a solid Compound 12 (9.0g, 21percent yield).

Reference： [1]Patent: CN105294670,2016,A .Location in patent: Paragraph 0255; 0256; 0257

34
[ 134450-56-9 ]
[ 135-67-1 ]
(PXZ)2PN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With tris-(dibenzylideneacetone)dipalladium(0); hydrogen; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In N,N-dimethyl-formamide; at 80℃;	Type (1-1) synthetic method of compound structure shown in the: lower range of the nitrogen, the 4,5-difluoro -1,2-dicyanobenzene is hydrogenated (5mmol), phenoxazine (18mmol), Pd2(dba)3(0.8mmol), NaOtBu (30mmol) and tBu3P·HBF4(0.8mmol) into 100 ml dimethyl formamide in the DMF 80 C temperature under stirring overnight. The 10 ml in cold water is added to the mixture the reaction quenching. After cooling to room temperature to be mixture, by vacuum filtration, then through the column chromatography purification product type (1-1), the product is dried in a vacuum. Yield: 69%.

Reference： [1]Patent: CN105418533,2016,A .Location in patent: Paragraph 0051; 0052; 0053; 0054

35
[ 89364-04-5 ]
[ 135-67-1 ]
C₁₇H₁₁N₃O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Reflux;	After the phenoxazine 20.0g (109.16mmol), 3-Bromo-4-nitro-pyridine 25.21 g (120.08mmol), the NaO (t-Bu) 15.73 g (163.75 mmol), the Pd 2 (dba) 3 2.99 g (3.27 mmmol) was suspended in the toluene 436 mL P (t-Bu) 31.58 mL (6.55 mmol) was put and it mixed reflux underthe nitrogen air current for 24 hours. It extracts in thedichloromethane and distilled water and the organic layer the silica gel is filtered. Hexane the organic solution is removed: it recrystallized as the dichloromethane andethyl acetate and it obtained the intermediate product(I) 23.33 g (yield : 70 %) by the dichloromethane = 7 :3 (v/v) after the silica gel column.

Reference： [1]Patent: KR2015/41508,2015,A .Location in patent: Paragraph 0183-0186

36
[ 19755-53-4 ]
[ 135-67-1 ]
C₁₇H₁₁N₃O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 24h;Inert atmosphere; Reflux;	After the phenoxazine 20.0g (109.16mmol), 2-Bromo-3-nitro-pyridine 25.21 g (120.08mmol), the NaO (t-Bu) 15.73 g (163.75 mmol), the Pd 2 (dba) 3 2.99 g (3.27 mmmol) was suspended in the toluene 436 mL P (t-Bu) 31.58 mL (6.55 mmol) was put and it mixed reflux underthe nitrogen air current for 24 hours. It extracts in thedichloromethane and distilled water and the organic layer the silica gel is filtered. Hexane the organic solution is removed: it recrystallized as the dichloromethane andethyl acetate and it obtained the intermediate product(K) 21.33 g (yield : 64 %) by the dichloromethane =7 : 3 (v/v) after the silica gel column.

Reference： [1]Patent: KR2015/41508,2015,A .Location in patent: Paragraph 0189-0192

37
[ 135-67-1 ]
[ 216312-73-1 ]
C₃₇H₂₆N₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 105℃;Inert atmosphere;	Type (1-1) synthetic method of compound structure shown in the: lower range of the nitrogen, the <strong>[216312-73-1]3,6-dibromo-9-fluorenone</strong> (5mmol), phenoxazine (18mmol), Pd2(dba)3(0.8mmol), NaOtBu (30mmol) and tBu3P HBF4 the (0.8mmol) into 100 ml toluene and the 105 C temperature under stirring overnight. The 10 ml in cold water is added to the mixture the reaction quenching. After cooling to room temperature to be mixture, by vacuum filtration, then through the column chromatography is purified to obtain product formula (1-1) compound of the structure shown in, the product is dried in a vacuum, yield: 80%.

Reference： [1]Patent: CN105503766,2016,A .Location in patent: Paragraph 0067; 0068; 0069; 0070

38
[ 135-67-1 ]
[ 25603-67-2 ]
C₅₀H₃₃NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With boron trifluoride diethyl etherate; In dichloromethane; at 25 - 30℃; for 2h;	To a 2L three-necked flask, <strong>[25603-67-2]9-phenyl-9-fluorenol</strong> (41.3g, 0.16mol), phenoxazine (14.7g, 0.08mol), and 500mL dichloromethane at 25-30C was added dropwise borontrifluoride etherate (BF3Et2O, 56.8g, 0.4mol). The reaction was incubated at 25-30C and stirred for 2 hours. 200mL of absolute ethanol was added to quench the reaction. It was wshed with deionized water, run through a slica gel column, solvent was removed, and recrystallized with toluene to give a pink solid intermediate a, yield 56%.

Reference： [1]Patent: CN105541747,2016,A .Location in patent: Paragraph 0041; 0042; 0044

39
[ 135-67-1 ]
[ 1028647-93-9 ]
C₃₆H₂₄N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 12h;Inert atmosphere; Reflux;	Dissolving the intermediate M-13 10.8g (27.0mmol) and phenoxazine 5g (27.0mmol), sodium t- butoxide 3.9g (40.5mmol) and tri -tert- butylphosphine 0.16g (0.81mmol) in 270ml toluene and, after inserting the Pd (dba) 2 0.15g (0.27mmol) and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After the reaction the organic layer was then extracted with ethyl ahseteyiteugwa dry distilled over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product n- hexane / dichloromethane (7: 3 by volume) as a column of silica gel for chromatographic purification of intermediates B-1 to give the desired compound as a white solid 12.4g (92% yield).
92%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 12h;Inert atmosphere; Reflux;	10.8 g (27.0 mmol) of the intermediate M-13, 5 g (27.0 mmol) of phenoxazine, 3.9 g (40.5 mmol) of sodium t-butoxide, and 0.16 g (0.81 mmol) of tri-tert-butylphosphine were dissolved in 270 ml of toluene, 0.15 g (0.27 mmol) of Pd(dba)2 was added thereto, and the mixture was agitated under a nitrogen atmosphere for 12 hours while being refluxed. When the reaction was complete, the resultant was extracted with ethyl acetate and distilled water, an organic layer obtained therefrom was dried with magnesium sulfate and filtered, and the filtered solution was concentrated under a reduced pressure. The concentrated product was purified with n-hexane/dichloromethane (7:3 of a volume ratio) through silica gel column chromatography, obtaining 12.4 g of a white solid compound, an intermediate B-1 (92% of a yield).

Reference： [1]Patent: KR101531614,2015,B1 .Location in patent: Paragraph 0887-0890
[2]Patent: KR101486562,2015,B1 .Location in patent: Paragraph 0894-0898

40
[ 108-86-1 ]
[ 135-67-1 ]
[ 37832-25-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene Reflux; Inert atmosphere;	Phenoxazine dissolved 30g (163.8mmol) and bromobenzene, 30.8g (196.6mmol), sodium t- butoxide 23.6g (245.8mmol) and tri -tert- butylphosphine 1.0g (4.92mmol) in 330ml toluene and , insert the Pd (dba) 2 0.94g (1.64mmol) and the mixture was stirred under reflux for 6 hours under a nitrogen atmosphere. After the reaction the organic layer was then extracted with ethyl ahseteyiteugwa dry distilled over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product n- hexane / dichloromethane (7: 3 by volume) to yield a column of silica gel 40.3 g (yield 95%) of intermediate M-1 chromatography to give the desired compound as a white solid.
95%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene for 6h; Inert atmosphere; Reflux;	Synthesis of Intermediate M-1 30 g (163.8 mmol) of phenoxazine, 30.8 g (196.6mmol) of bromobenzene, 23.6 g (245.8 mmol) of sodiumt-butoxide, and 1.0 g (4.92 mmol) of tri-tert-butylphosphinewere dissolved in 330 ml of toluene, 0.94 g (1.64 mmol) of Pd(dba)2 was added thereto, and the mixture was agitated for 6 hours under a nitrogen atmosphere while being reuxed. When the reaction was complete, the resultant was extracted with ethyl acetate and distilled water, an organic layer obtained there from was dried with magnesium sulfate and filtered, and the filtered solution was concentrated under a reduced pressure. Then, the concentrated product was purified with n-hexane/dichloromethane (713 of a volume ratio) through silica gel column chromatography, obtaining 40.3 g of a white solid compound, an intermediate M-1 (95% of a yield).
93%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;

76.8%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene at 120℃; for 48h; Inert atmosphere;
23%	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II)-methyl tert-butyl ether adduct; sodium tertiary butoxide; dicyclohexyl(2′,6′-diisopropoxy-[1,1′-biphenyl]-2-yl)phosphine In 1,4-dioxane at 130℃; for 48h; Inert atmosphere;
23%	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II)-methyl tert-butyl ether adduct; sodium tertiary butoxide; dicyclohexyl(2′,6′-diisopropoxy-[1,1′-biphenyl]-2-yl)phosphine In 1,4-dioxane at 130℃; for 48h; Glovebox; Inert atmosphere;	e 10-Phenylphenoxazine A 50 mL storage flask was charged with a stir bar, flame dried under vacuum and back filled with nitrogen three times. The flask was then charged with phenoxazine (183 mg, 1.0 mmol, 1.00 eq.), NaOtBu (192.2 mg, 2.0 mmol, 2.00 eq.), and RuPhos (12 mg, 0.03 mmol, 0.03 eq.). The flask was taken into a nitrogen filled glovebox where RuPhos Precat (21 mg, 0.03 mmol, 0.03 eq.), 1 mL dry dioxane and bromobenzene (0.11 mL, 2.0 mmol 2.00 eq.) were added. The flask was placed in an oil bath at 130° C. while stirring for 48 hours. The flask was then cooled to room temperature, diluted with CH2Cl2, and the solution was washed with water three times, brine once, dried over MgSO4 and purified by recrystallization from CH2Cl2 layered with hexanes at -25° C. to give 60 mg of yellow crystals, 23% yield.
	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 110℃; Inert atmosphere;
	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene at 110℃; for 24h; Inert atmosphere;	1.1 (1) Synthesis of intermediate product 1: Under a nitrogen atmosphere, add 183 to a 250 ml wide-mouth three-neck round bottom reaction bottle. Milligram of phenoxazine and 10 ml of bromobenzene were dissolved in 70 ml of toluene solution. Then 5 g of potassium carbonate was added and agitated for 15 minutes. Subsequently, 44.6 mg of palladium acetate and 0.73 mg of tri-tert-butylphosphine solution were added, agitated for 30 minutes, and then heated to 110 degrees Celsius. The reaction was refluxed for 24 hours. After the reaction was stopped and the reaction was stopped, the reaction system liquid was removed by rotary evaporation to obtain the intermediate product 10-phenyl-10H-phenoxazine.
	With tri-tert-butyl phosphine; palladium diacetate; sodium tertiary butoxide In toluene at 110℃; for 12h; Inert atmosphere;	4 Synthesis method of 10-phenyl-phenoxazine (PXZ-Ph) (see Figure 4) Phenoxazine, bromobenzene, sodium tert-butoxide, catalyst palladium acetate and ligand P(tBu)3 are dissolved in toluene solution, and after cyclic degassing treatment, the reaction is heated at 110°C under nitrogen for 12 hours. After cooling at room temperature, the reaction mixture of the previous step was extracted with dichloromethane, the extracted organic phase was collected and dried with anhydrous MgSO4, and the crude product was purified by silica gel column chromatography to obtain a white solid.

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR101531614, 2015, B1 Location in patent: Paragraph 0787-0790
[2]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR101486562, 2015, B1 Location in patent: Paragraph 0794-0798
[3]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[4]McCarthy, Blaine G.; Pearson, Ryan M.; Lim, Chern-Hooi; Sartor, Steven M.; Damrauer, Niels H.; Miyake, Garret M. [Journal of the American Chemical Society, 2018, vol. 140, # 15, p. 5088 - 5101]
[5]Pearson, Ryan M.; Lim, Chern-Hooi; McCarthy, Blaine G.; Musgrave, Charles B.; Miyake, Garret M. [Journal of the American Chemical Society, 2016, vol. 138, # 35, p. 11399 - 11407]
[6]Current Patent Assignee: COLORADO STATE UNIVERSITY SYSTEM; UNIVERSITY OF COLORADO (SYSTEM) - US2018/237550, 2018, A1 Location in patent: Paragraph 0131
[7]Karimata, Ayumu; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji [RSC Advances, 2017, vol. 7, # 88, p. 56144 - 56152]
[8]Current Patent Assignee: SOUTH CHINA UNIVERSITY OF TECHNOLOGY - CN108530376, 2018, A Location in patent: Paragraph 0028; 0030; 0031
[9]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN112625004, 2021, A Location in patent: Paragraph 0038; 0104-0106

41
[ 5394-23-0 ]
[ 135-67-1 ]
4,7-diphenoxazin-N-yl-1,10-phenanthroline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%		The 1.30 g phenoxazine,And 240 mg of sodium hydride 70% oil dispersion of20 ml of tetrahydrofuran was added 50 ml single-necked round-bottomed flask,Was added 0.75 g After refluxing under argon for 30 minutes<strong>[5394-23-0]4,7-dichloro-1,10-phenanthroline</strong>,Then refluxed for 24 hours at 60 C,After cooling to room temperature, quenched with saturated brine,Extracted with dichloromethane,The organic phase was dried over anhydrous sodium sulfate,Too, spin dry. Methanol: dichloromethane 1:30 by volume through the column to give the product 1.40 g. A pale yellow solid, yield 86%.

Reference： [1]Patent: CN105859714,2016,A .Location in patent: Paragraph 0038; 0039; 0040; 0041

42
[ 135-67-1 ]
[ 623-00-7 ]
4-(10H-phenoxazin-10-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;
80%	With palladium diacetate; sodium tertiary butoxide; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 110℃; for 24h; Inert atmosphere;
76%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene for 5h; Reflux;	5 Synthesis of Compound 100 The 4-bromophenyl cyanide (3.62g, 20mmol),10 hydrogen-phenoxazine (2.75 g, 15 mmol)Palladium acetate (0.4 g, 1.98 mmol)Potassium carbonate (4.14 g, 30 mmol)And tert-butylphosphine (0.5 g, 2.4 mmol)Dissolved in toluene,Reflux and stir for 5 hours,Vacuum drying evaporated toluene,The solid was then dissolved in ethyl acetate,Stirring, filtering,Washed with saturated salt 3 times,The solvent was evaporated to dryness under a vacuum steaming apparatus,Purification by silica gel column chromatography,To obtain solid compound 100 (4.5 g, 11.4 mmol)Yield 76%.

73%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide; dicyclohexyl(2’,4’,6’-triisopropyl-[ 1,1’-bi-phenyl]-2-yl)phosphane In toluene at 110℃; for 15h; Inert atmosphere;
64%	With copper (I) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	2-3 2-3: synthesis of 4-(10H-phenoxazin-10-yl)benzonitrile 10H-phenoxazine (4.5 g, 24.5 mmol) and 4-bromobenzonitrile (4.92 g, 27.02 mmol) and CuI (1.87 g, 9.83 mmol) ,18-crown-6 (0.65 g, 2.46 mmol), K2CO3 (13.58g, 98.25mmol) andO- dichlorobenzenePut together with (30ml) was stirred for 24 hours at 180oC. After completion of the reaction remove the solvent, which was then extracted with water and ethyl acetate, dried over MgSO4, the product was separated by column chromatography Griffey (n- hexane / EtOAc = 2/1). The yield was 64% (4.5g).
25%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene at 120℃; for 24h; Inert atmosphere;	2.2.2 General procedure for Buchwald- Hartwig cross-coupling for compounds 2 and 4 General procedure: A mixture of phenothiazine 5 or phenoxazine 6 (1.0 eq.), 4-bromobenzonitrile 8 (1.2 eq.), K2CO3 (5.0 eq.), Pd(OAc)2 (0.2 eq.), P(t-Bu)3 (0.3 eq.) and dry toluene (20mL) were stirred at 120°C in nitrogen atmosphere for 24h. After cooling, water was added and the product was extracted with ethyl acetate (2×30mL). The organic layer was washed with brine solution and dried over anhydrous MgSO4. After filtration, the solvent was removed under vacuum and the residue was purified by column chromatography using a mixture of petroleum ether/CH2Cl2 (8:2) as eluent.

Reference： [1]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[2]Wei, Danqing; Ni, Fan; Wu, Zhongbin; Zhu, Zece; Zou, Yang; Zheng, Kailu; Chen, Zhanxiang; Ma, Dongge; Yang, Chuluo [Journal of Materials Chemistry C, 2018, vol. 6, # 43, p. 11615 - 11621]
[3]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN106831633, 2017, A Location in patent: Paragraph 0137; 0138; 0139; 0140
[4]Qu, Yangyang; Pander, Piotr; Bucinskas, Audrius; Vasylieva, Marharyta; Tian, Yayang; Miomandre, Fabien; Dias, Fernando B.; Clavier, Gilles; Data, Przemyslaw; Audebert, Pierre [Chemistry - A European Journal, 2019, vol. 25, # 10, p. 2457 - 2462]
[5]Current Patent Assignee: KOREA UNIVERSITY - KR101489184, 2015, B1 Location in patent: Paragraph 0057; 0118-0120
[6]Baraket, Faiza; Pedras, Bruno; Torres, Érica; Brites, Maria João; Dammak, Mohamed; Berberan-Santos, Mário N. [Dyes and Pigments, 2020, vol. 175]

43
[ 135-67-1 ]
[ 91371-12-9 ]
C₃₆H₂₂N₄O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 8h;Inert atmosphere; Reflux;	2,2 '- dinitro _4,4' - dibromo biphenyl (20g, 49.8mmol), phenoxazine (18.4g, 100.4mmol), palladium acetate (1. 2g, 5 4mmol.), Tri tributylphosphine (1. 6g, 7. 8mmol) and cesium carbonate (48. 6g, 49.4mmol) was dissolved in toluene, under a nitrogen atmosphere, the reaction was heated at reflux for 8 hours. The solvent was evaporated in vacuo, the remaining material was stirred in pentane was added, filtered, purified by silica gel column chromatography, to obtain a solid compound 61-a (16. 0g, 53%).

Reference： [1]Patent: CN105399696,2016,A .Location in patent: Paragraph 0172-0175

44
[ 135-67-1 ]
[ 331-61-3 ]
10-(3-fluoro-4-methoxybenzyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
41%	With sodium hydride; In N,N-dimethyl-formamide; at 0 - 20℃; for 24h;Inert atmosphere;	General procedure: Under inert atmosphere, the sodium hydride (1.1 equiv.) was added to a solution of amine derivative 19-23 (1.1 equiv.) in DMF at 0 C. The benzyl bromide 15-18 (1 equiv.) was then added immediately and the reaction was stirred for 24 h. The mixture was then washed with water and extracted with methylene chloride. The organic phase was dried over MgSO4 and purified by flash chromatography (n-heptane/EtOAc, gradient from 100/0 to 0/100) to give pure compounds 5-14.

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 6021 - 6030

45
[ 135-67-1 ]
[ 580-13-2 ]
10-(naphthalen-2-yl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;
69%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene at 110℃; for 24h; Inert atmosphere; Sealed tube;
68%	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II)-methyl tert-butyl ether adduct; sodium tertiary butoxide; dicyclohexyl(2′,6′-diisopropoxy-[1,1′-biphenyl]-2-yl)phosphine In 1,4-dioxane at 100℃; for 16h; Schlenk technique; Inert atmosphere;

53%	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II)-methyl tert-butyl ether adduct; sodium tertiary butoxide; dicyclohexyl(2′,6′-diisopropoxy-[1,1′-biphenyl]-2-yl)phosphine In 1,4-dioxane at 130℃; for 48h; Glovebox; Inert atmosphere;	e 2-Naphthalene-10-phenoxazine, or 10-(naphthalen-2-yl)-10H-phenoxazine A 100 mL storage flask was charged with a stir bar, flame dried under vacuum then back filled with nitrogen three times. The flask was then charged with phenoxazine (1.00 g, 5.46 mmol, 1.00 eq.), NaOtBu (1.054 g, 10.92 mmol, 2.00 eq.), and RuPhos (65.6 mg, 0.16 mmol, 0.03 eq.). The flask was taken into a nitrogen filled glovebox where RuPhos Precat (114.75 mg, 0.16 mmol, 0.03 eq.), 6 mL dry dioxane and 2-bromonaphthalene (2.26 mg, 10.92 mmol, 2.00 eq.) were added. The flask was placed in an oil bath at 130° C. while stirring for 48 hours. The flask was then cooled to room temperature, diluted with CH2Cl2, and the solution was washed with water three times, brine, dried over MgSO4 and purified by recrystallization from CH2Cl2 at -25° C. to yield 890 mg of light yellow, flakey crystals, 53% yield. Final purification was conducted via sublimation at 100 mTorr at 195° C. 1H NMR (CDCl3, 400 MHz) δ 8.08 (d, J=8.60 Hz, 1H), 7.95 (d, J=7.00 Hz, 1H), 7.88 (m, 2H), 7.57 (m, 2H), 7.42 (dd, J=8.64, 2.04 Hz, 1H), 6.73 (dd, J=7.84, 1.56 Hz, 2H), 6.66 (t, J=7.52, 2H), 6.57 (td, J=8.12, 1.60 Hz, 2H), 5.99 (d, J=7.96, 2H). 13C NMR (CDCl3, 400 MHz) δ 144.42, 136.74, 135.06, 134.78, 133.28, 131.55, 130.29, 128.23, 128.15, 127.12, 126.78, 123.49, 121.66, 115.74, 113.78. HRMS (ESI): calculated for M+ C22H15NO, 309.1154; observed 309.1151.
	With chloro(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II)-methyl tert-butyl ether adduct; sodium tertiary butoxide; dicyclohexyl(2′,6′-diisopropoxy-[1,1′-biphenyl]-2-yl)phosphine In 1,4-dioxane at 130℃; for 48h; Inert atmosphere;

Reference： [1]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[2]McCarthy, Blaine G.; Pearson, Ryan M.; Lim, Chern-Hooi; Sartor, Steven M.; Damrauer, Niels H.; Miyake, Garret M. [Journal of the American Chemical Society, 2018, vol. 140, # 15, p. 5088 - 5101]
[3]Bhattacherjee, Aditi; Sneha, Mahima; Lewis-Borrell, Luke; Amoruso, Giordano; Oliver, Thomas A.A.; Tyler, Jasper; Clark, Ian P.; Orr-Ewing, Andrew J. [Journal of the American Chemical Society, 2021, vol. 143, # 9, p. 3613 - 3627]
[4]Current Patent Assignee: COLORADO STATE UNIVERSITY SYSTEM; UNIVERSITY OF COLORADO (SYSTEM) - US2018/237550, 2018, A1 Location in patent: Paragraph 0137
[5]Pearson, Ryan M.; Lim, Chern-Hooi; McCarthy, Blaine G.; Musgrave, Charles B.; Miyake, Garret M. [Journal of the American Chemical Society, 2016, vol. 138, # 35, p. 11399 - 11407]

46
[ 135-67-1 ]
3-bromo-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With NBS In tetrahydrofuran at 0 - 20℃; for 3h;	2.1 Step 1: 10H-phenoxazine (10 g, 54.6 mmol) was dissolved in anhydrous tetrahydrofuran (212.87 ml), and then N-bromosuccinimide (9.321 g, 51.9 mmol) was slowly added at 0 °C, stirred for 3 hours, and column chromatography. The product is obtained through photography (yield: 54%).
49.1%	With NBS In N,N-dimethyl-formamide at 0℃; for 6.5h;	9.9-1 Synthesis Example 9-1. Synthesis of <9-a> While purging with nitrogen gas in a 1L round bottom flask at room temperature,Phenoxazine (50.0 g, 273 mmol),400 mL of dimethylformamide was added and cooled to 0 ° C.N-bromosuccinimide solution (3.0M in DMF solution) (100mL, 300mmol)Add for 30 minutesStir for 6 hours.After TLC confirms the end of the reaction,Add distilled water.The solid obtained by filtration was purified by silica gel column chromatography to obtain <9-a>(35.1 g, 134 mmol).(Yield 49.1%)
46%	With NBS In tetrahydrofuran at 0℃; for 1h; Darkness; Inert atmosphere;

38%	With NBS In tetrahydrofuran at 0℃; for 3h; Cooling with ice;
19%	With NBS In tetrahydrofuran at 20℃; for 1.5h; Cooling with ice;	7 Synthesis of Intermediate Product 7-1 While cooling with ice, phenoxazine (31.1 g, 170 mmol) was added to tetrahydrofuran (600 mL), and a N-bromosuccinimide (30.2 g, 170 mmol) tetrahydrofuran (450 mL) solution was gradually added dropwise to the resultant mixture. After the dropwise addition, the resultant was returned to room temperature, and was stuffed for 1.5 hours. After adding ethyl acetate to the reaction solution, an organic layer was washed with water. After drying the resultant with anhydrous sodium sulfate, the drying agent was separated through filtration. The residue obtained by removing the solvent under reduced pressure was purified by silica gel column chromatography (stationary phase: neutral silica gel, mobile phase: ethyl acetate/hexane), to therebyobtain Intermediate Product 7-1 (yielded amount: 25.6 g, yield: 19% by mass).
	With NBS In tetrahydrofuran at 20℃; for 1h;	1 1 mol of compound A-1 was added to THF, and 1 mol of NBS solution in THF was added dropwise. The reaction was completed at room temperature for 1 h. After completion of the reaction, the THF was dried and the crude product was passed through a silica gel column to give product 456 mmol A.
12.8 g	With NBS In chloroform; N,N-dimethyl-formamide at 20℃; for 18h;	Synthesis of Intermediate 1-6 Phenoxazine (20 g, 109.16 mmol) was added to a mixed solution of a chloroform (200 ml) and dimethyl formamide (50 ml). N-bromosuccinimide (1 equivalent) was added thereto, and the obtained mixture was stirred at room temperature for 18 hours. Subsequently, a 1 M sodium thiosulfate solution (100 mE) was added to the reaction solution to separate layers, and an organic layer was separated therefrom. The organic layer was concentrated, and the concentrated residue was purified through silica gel colunm by using hexane and ethylacetate as an eluting solvent to obtain Intermediate 1-6 (12.8 g).
	With NBS In N,N-dimethyl-formamide at 0℃;	Phenoxazine (12.8g, 75mmol), N-bromosuccinimide (NBS) (14.5g, 80mmol) and N,N-dimethylformamide (DMF) were mixed at 0°C for bromination reaction, to obtain 3-bromophenoxazine;

Reference： [1]Current Patent Assignee: KOREA NATIONAL UNIVERSITY OF TRANSPORTATION INDUSTRY - KR2020/116722, 2020, A Location in patent: Paragraph 0180-0184
[2]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR102004386, 2019, B1 Location in patent: Paragraph 0310-0316
[3]Arnott, Gareth E.; Loots, Leigh; Olivier, Tania; Reader, Janette; de Villiers, Katherine A.; de Villiers, Marianne; Birkholtz, Lyn-Marié; Kok, Michélle [ChemMedChem, 2022, vol. 17, # 10]
[4]Abe, Jiro; Kobayashi, Yoichi; Mutoh, Katsuya; Okajima, Hajime; Sakamoto, Akira; Usui, Ryosuke; Yamamoto, Katsuya [Journal of the American Chemical Society, 2020, vol. 142, # 22, p. 10132 - 10142]
[5]Current Patent Assignee: RICOH CO LTD - WO2016/203773, 2016, A1 Location in patent: Page/Page column 0141; 0142
[6]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN106946934, 2017, A Location in patent: Paragraph 0044-0046
[7]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2018/291264, 2018, A1 Location in patent: Paragraph 0137; 0138
[8]Current Patent Assignee: UNIV YUNNAN - CN114149368, 2022, A Location in patent: Paragraph 0118; 0124

47
[ 135-67-1 ]
[ 2268-05-5 ]
10-(2,6-dichlorophenyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium phosphate; In N,N-dimethyl-formamide; for 16h;Reflux;	lOg (54.6 mmol) Phenoxazine, 14.2 g (82 mmol) 1,3-dichloro-2-fluoro- benzene and 25 g (0.11 mol) potassium phosphate were dissolved in 250 mL DMF and stirred 16 hours at reflux. After cooling down to roomtemperature 300 ml toluene and 500 ml water was added and the phaseswere separated. The organic phase was washed with water (3x300 ml) and the aqueous phase was extracted two times with toluene. The combined organic phases were reduced to dryness and purified by recrystallizationfrom toluene/heptane.Yield: 16 g (0.05 mol; 90 %)

Reference： [1]Patent: WO2017/28941,2017,A1 .Location in patent: Page/Page column 64

48
[ 135-67-1 ]
[ 2268-05-5 ]
C₃₀H₂₁NO [ No CAS ]

Reference： [1]Patent: WO2017/28941,2017,A1

49
[ 135-67-1 ]
[ 350-46-9 ]
[ 58736-93-9 ]

Yield	Reaction Conditions	Operation in experiment
92%	With cesium fluoride In dimethyl sulfoxide at 120 - 140℃; Inert atmosphere;	1.1 (1) Preparation of 10-(4-nitrophenyl)phenoxazine: Weigh 16.4 mmol of phenoxazine,17.2 mmol 4-fluoronitrobenzene and 17.2 mmol cesium fluoride,Dissolved in 30mL of dry dimethyl sulfoxide,In a nitrogen atmosphere, the mixture was heated and stirred at 120 ° C for 18 hours.Then cooled to room temperature, poured into a mixed solution of ethanol and deionized water, filtered,Washing with water to give 10-(4-nitrophenyl)phenoxazine, Red solid, 92% yield;
77%	With cesium fluoride In dimethyl sulfoxide at 130℃; for 20h; Inert atmosphere;	1.1 Preparation of 4,4'-diamino-4"-N-phenoxazine triphenylamine To a 250 mL three-necked flask equipped with a mechanical stirrer, add 10g (54.6mmol) of the phenoxazine, 8.2g (57.3mmol) of the P-nitrophenyl, 4.4g (28.7mmol) cesium fluoride of, adding 100 ml of dimethyl sulfoxide as solvent, in the stirring, under the protection of nitrogen, for 130 °C reaction 20h; discharge after cooling in ice water and ethanol volume ratio of 1:1 and fully in the mixed solution of stirring, the crude product is used N, N-dimethyl formamide and water recrystallization, get 12.8g red N-(4-nitrophenyl) phenoxazine solid, yield is 77%.
70%	With potassium carbonate In dimethyl sulfoxide at 120℃; for 21h; Inert atmosphere; Schlenk technique;	N-(4-nitrophenyl)phenoxazine (1a). In a 100 mL three-neckedround-bottomed flask equipped with a magnetic stirring bar, nitrogeninlet and outlet and condenser, 4-fluoro-nitrobenzene (2.3 g,16.4 mmol), 10H-phenoxazine (2 g, 10.1 mmol), potassium carbonate(2.26 g, 16.4 mmol) and DMSO (30 mL) were placed. The reactionmixture was refluxed at 120 °C overnight (21 h) when the solution becamedark-red. The reaction evolution was monitored by thin layerchromatography (TLC) using hexane/ethyl acetate, 30/1, v/v. When10H-phenoxazine was no longer present, the reaction mixture was allowedto cool to room temperature and slowly poured into 150 mL ofstirred methanol when an orange-red solid started to precipitate. It wascollected by filtration and washed thoroughly with methanol/water.The resulting nitro compound 1a was dried under vacuum to obtain2.15 g of orange-red powder (70% yield).2.15 g of orange-red powder (70% yield).1H NMR (DMSO, 400 MHz), δ (ppm): 8.49-8.47 (d, 2H), 7.77-7.75(d, 2H), 6.83-6.70 (m, 6H), 6.05-6.05 (d, 2H).13C NMR (DMSO, 400 MHz), : (ppm): 146.71, 144.97, 143.52,132.82, 131.37, 126.51, 123.76, 122.38, 115.66, 113.94.

Reference： [1]Current Patent Assignee: ZHENGZHOU UNIVERSITY - CN110437172, 2019, A Location in patent: Paragraph 0048-0053
[2]Current Patent Assignee: JILIN UNIVERSITY - CN105884707, 2016, A Location in patent: Paragraph 0041-0042
[3]Damaceanu, Mariana-Dana; Constantin, Catalin-Paul; Bejan, Andra-Elena; Mihaila, Mihai; Kusko, Mihaela; Diaconu, Cristian; Mihalache, Iuliana; Pascu, Razvan [Dyes and Pigments, 2019, vol. 166, p. 15 - 31]

50
[ 135-67-1 ]
[ 57774-35-3 ]
C₂₅H₁₆N₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; for 5h;Reflux;	45c (3.86 g, 15 mmol),10 hydrogen-phenoxazine (2.75 g, 15 mmol)Palladium acetate (0.4 g, 1.98 mmol)Potassium carbonate (4.14 g, 30 mmol)And tert-butylphosphine (0.5 g, 2.4 mmol)Dissolved in toluene,Reflux and stir for 5 hours,Vacuum drying evaporated toluene,The solid was then dissolved in ethyl acetate,Stir, filter, washed with saturated brine 3 times,The solvent was evaporated to dryness under a vacuum steaming apparatus,Purification by silica gel column chromatography,To obtain solid compound 45 (3.76 g, 10 mmol)Yield 67%.

Reference： [1]Patent: CN106831633,2017,A .Location in patent: Paragraph 0117; 0122; 0123

51
[ 135-67-1 ]
[ 56341-31-2 ]
C₂₅H₁₅NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 5h;Reflux;	The compound 31-a (5.5g, 18.1mmol), phenoxazine (3.6g, 20mmol), palladium acetate (0.4g, 1.98mmol), cesium carbonate (12.6g, 36mmol) and tert-butyl phosphate (0.5g, 2.4 mmol) was dissolved in toluene, and stirred at reflux for 5 hours. Toluene was evaporated to dryness and dried in vacuo, and the solid was dissolved in ethyl acetate, stirred, filtered, washed with brine 3 times. Rotavapor under vacuum and the solvent evaporated to dryness. It was purified by silica gel column chromatography to obtain a solid compound 31 (4g, 10.5mmol), 58% yield.

Reference： [1]Patent: CN106831744,2017,A .Location in patent: Paragraph 0131; 0132

52
[ 135-67-1 ]
[ 40000-20-2 ]
C₂₄H₁₅N₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 10h;Inert atmosphere; Reflux;	Synthesis of Compound 57: The compound 57a (3.9 g, 15.0 mmol),Phenoxazine (2.9 g, 16 mmol),Tert-butylphosphine (0.35 g, 2 mmol),Palladium acetate (0.4 g, 1.8 mmol) and cesium carbonate (9.7 g, 30 mmol) were dissolved in toluene,Under a nitrogen atmosphere,The reaction was heated under reflux for 10 hours.The solvent was evaporated in vacuo,The remaining material was stirred with pentane,filter,Purification by silica gel column chromatography,To obtain solid compound 5, (3.7 g, 10.2 mmol),Yield 62percent.

Reference： [1]Patent: CN106831743,2017,A .Location in patent: Paragraph 0124; 0125; 0126; 0127

53
[ 135-67-1 ]
[ 156492-30-7 ]
4,7-diphenoxazin-N-yl-1,10-phenanthroline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate; In toluene; for 10h;Inert atmosphere; Reflux;	The compound 73d (5.1 g, 15.0 mmol),Phenoxazine (5.8 g, 32 mmol)Tert-butylphosphine (0.35 g, 2 mmol),Palladium acetate (0.4 g, 1.8 mmol) and cesium carbonate (19.5 g, 60 mmol) were dissolved in toluene,Under a nitrogen atmosphere,The reaction was heated under reflux for 10 hours.The solvent was evaporated in vacuo,The remaining material was stirred with pentane,filter,Purification by silica gel column chromatography,To obtain solid compound 5, (5.31 g, 9.8 mmol)Yield 65%.

Reference： [1]Patent: CN106831743,2017,A .Location in patent: Paragraph 0129; 0135; 0136

54
[ 135-67-1 ]
[ 216312-73-1 ]
C₃₇H₂₂N₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; for 10h;Reflux;	250 ml three-neck bottle, in an atmosphere of nitrogen, adding 0.01 muM (3.38 g) 3, 6 - dibromo -9 - fluorenone, 0.025 muM (4.58 g) compound M1, 0.03mol (2.88 g) tert sodium butylate, 10-4Mol (0.073 g) Pd (dppf) Cl2, 180 ml toluene, heating reflux for 10 hours, sampling board, the reaction is complete; natural cooling, filtering, collecting the filtrate to carry out decompression and steaming and (-0.09 mpa, 85 C), to column chromatography, to obtain the target product, purity 99%, yield 73%.

Reference： [1]Patent: CN107056701,2017,A .Location in patent: Paragraph 0110; 0111; 0112; 0113; 0114

55
[ 135-67-1 ]
[ 106-37-6 ]
[ 71041-21-9 ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); sodium tertiary butoxide; In toluene; at 115℃; for 24h;Inert atmosphere;	In a 250 mL three-necked flask, under nitrogen protection,Adding 0.03 mol phenoxazine,0.036 mol of 1,4-dibromobenzene, 150 mL of toluene, stirred and mixed,Then 0.09 mol of sodium tert-butoxide was added,0.002 molPd2 (dba) 3,Heated to 115 C with stirring,Reflux reaction for 24 hours; natural cooling to room temperature, filtration,The filtrate was distilled under reduced pressure to a non-distillate column over neutral silica to give intermediate III
	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; at 110℃; for 24h;Inert atmosphere;	Under a nitrogen atmosphere, Add 183 mg of phenoxazine and 10 ml of p-dibromobenzene to a 250 ml three-neck round bottom reaction flask. Dissolved in 70 ml of toluene solution. Then 5 g of potassium carbonate was added and agitated for 15 minutes. Subsequently, 44.6 mg of palladium acetate and 0.73 ml of tri-tert-butylphosphine solution, Stir for 30 minutes with aeration. It was then heated to 110 C and refluxed for 24 hours. The reaction system liquid was removed by rotary evaporation to give the intermediate product 10-(4-bromophenyl)-10H-phenoxazine.

Reference： [1]Organometallics,2022,vol. 41,p. 509 - 513
[2]Patent: CN107226811,2017,A .Location in patent: Paragraph 0058; 0060
[3]Patent: CN108530376,2018,A .Location in patent: Paragraph 0082; 0084; 0085

56
[ 135-67-1 ]
[ 864377-28-6 ]
C₃₄H₂₃N₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene Reflux;

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/101586, 2017, A Location in patent: Paragraph 0169

57
[ 135-67-1 ]
[ 94994-62-4 ]
C₃₀H₂₀N₂O [ No CAS ]

Reference： [1]Patent: KR2017/101586,2017,A .Location in patent: Paragraph 0170

58
[ 135-67-1 ]
[ 57103-20-5 ]
C₄₂H₂₇N₃O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With copper; potassium carbonate; In 1-methyl-pyrrolidin-2-one; for 48h;Inert atmosphere; Reflux;	Under nitrogen protection,Intermediate a obtained in Intermediate Preparation Example (3.61 g, 9 mmol)And phenoxazine (4.12 g, 22.5 mmol)Dissolved in 50 mL of NMP (N-methylpyrrolidone)Then catalyst copper (1.72 g, 27 mmol)Acid-binding agent and potassium carbonate (4.97g, 36mmol).The system was warmed to reflux for 48 hours,Natural cooling to 20 ~ 25 after adding 100mL water quenching reaction,The product was filtered to give the crude product.The crude product was purified by silica gel column chromatography,The eluent was dichloromethane: n-hexane = 1: 7 (V / V),A white powder is obtained. The resulting powder is further sublimated and purified by a chemical vapor deposition system at a sublimation temperature of 225 ° C to obtain the compound C01 in a yield of 63percent.

Reference： [1]Patent: CN105175405,2017,B .Location in patent: Paragraph 0051-0054

59
[ 135-67-1 ]
[ 29898-32-6 ]
C₁₈H₁₁Cl₂NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; calcium carbonate In tetrahydrofuran; water for 1.5h;	2 Preparation of compound IM-7 SM1 (50 g, 0.27 mol) and 2,4-dichloro-1-iodobenzene (82 g, 0.3 mol) were dissolved in tetrahydrofuran (THF) , And an aqueous solution of calcium carbonate was added thereto. Tetrakis- (triphenylphosphine) palladium (0.95 g, 0.0008 mol) was added and the mixture was stirred for 1.5 hours while boiling. Thereafter, the reaction mixture was cooled to room temperature, and the organic layer was separated. The organic layer was recrystallized from chloroform and ethanol to obtain a compound IM-3 solid (62 g, yield 69%).

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/139350, 2017, A Location in patent: Paragraph 0134-0136

60
[ 135-67-1 ]
2,3-bis(4′-bromophenyl)-6,7-difluoroquinoxaline [ No CAS ]
10,10'-((6,7-difluoroquinoxaline-2,3-diyl)bis(4,1-phenylene))bis(10H-phenoxazine) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 48h;	3 Example 3: Preparation of Compound I-2-2 Intermediate 2 (1.2 g, 2.52 mmol), phenoxazine (1.06 g, 5.79 mmol), sodium tert-butoxide (0.58 g, 6.04 mmol), palladium acetate (0.023 g, 0.10 mmol), tri-tert-butylphosphine Tetrafluoroborate (0.088g, 0.30mmol) and 40mLToluene was added to a 100 mL round bottom flask, refluxed at 110 ° C for 48 hours, and then quenched with 10 mL of saturated aqueous sodium chloride solution.The reaction is first extracted with dichloromethane, dried over anhydrous sodium sulfate, and finally treated with dichloromethane/petroleum ether (v/v = 2:3).The eluent was separated by silica gel column chromatography. The product was a yellow powder with a yield of 95%.
93%	With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene Reflux; Inert atmosphere;
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 100℃; Inert atmosphere;	2 In a 150 mL three-necked flask, 1.00 g (2.10 mmol) 2,3-bis(4-bromophenyl)-6,7-difluoroquinoxaline,0.80 g (4.36 mmol) 10H-phenoxazine, 1.00 g (10.4 mmol) sodium tert-butoxide, 0.032 g (0.11 mmol) tri-tert-butylphosphine tetrafluoroborate,0.10 g (0.11 mmol) tris(dibenzylideneacetone)dipalladium(0), then add 50 mL toluene as a solvent, and heat the reaction at 100 under nitrogen protection;After the reaction is completed, after extraction with 100 mL of dichloromethane, the organic phases are combined and filtered with suction. The product is separated and purified by column chromatography (petroleum ether/dichloromethane, volume ratio 1:2).An orange solid 10,10'-(((6,7-difluoroquinoxaline-2,3-diyl)bis(4,1-phenylene))bis(10H-phenoxazine) was obtained in a yield Is 80%

Reference： [1]Current Patent Assignee: WUHAN UNIVERSITY - CN106047337, 2018, B Location in patent: Paragraph 0087; 0088; 0089
[2]Yu, Ling; Wu, Zhongbin; Xie, Guohua; Zhong, Cheng; Zhu, Zece; Ma, Dongge; Yang, Chuluo [Chemical Communications, 2018, vol. 54, # 11, p. 1379 - 1382]
[3]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN112079843, 2020, A Location in patent: Paragraph 0044; 0045

61
[ 15862-18-7 ]
[ 135-67-1 ]
C₃₄H₂₂N₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 100℃; for 24h;	4,4'-Dibromobipyridine (3.14 g, 10 mmol), phenoxazine (4.40 g, 24 mmol), bis(dibenzylideneacetone) palladium (Pd(dba)2, 0.46 g, 0.8 mmol), sodium tert-butoxide (NaOt-Bt, 2.88 g, 30 mmol), and tri(tert-butyl)phosphonium tetrafluoroborate (tBu3P.HBF4, 0.116 g, 0.4 mmol) were added to 50 mL of dehydrated toluene, and heated for 24 hours while maintaining the inner temperature to 100C. After the reaction liquid was allowed to cool, 200 mL of water was added thereto, and the mixture was separated. The organic layer was concentrated, and the concentrate was purified by SiO2 column chromatography with a mixed solvent of chloroform and hexane (1/1) as a developing solvent. According to the procedures, the compound 1 was obtained at a yield amount of 3.10 g and a yield of 60%. The purified product of the compound 1 was further subjected to sublimation purification under condition of 320C. and 1 Pa or less. (0131) 1H NMR (600 MHz, CDCl3) delta 8.9-8.5 (2H), 7.8-7.5 (2H), 7.4-6.8 (18H); MS (70 eV, EI) m/z=518 (M+)

Reference： [1]Patent: US9935272,2018,B2 .Location in patent: Page/Page column 62-63

62
[ 135-67-1 ]
[ 18511-71-2 ]
C₃₄H₂₂N₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 100℃; for 24h;	The synthesis process and the purification by column chromatography were performed in the same manner as in Synthesis Example 1 except that 5,5'-dibromobipyridine (3.14 g, 10 mmol) was used instead of 4,4'-dibromobipyridine (3.14 g, 10 mmol), and thus the compound 4 was obtained at a yield amount of 2.33 g and a yield of 45%. Thereafter, the purified product of the compound 4 was subjected to sublimation purification under condition of 320C. and 1 Pa or less. (0140) 1H NMR (600 MHz, CDCl3) delta 8.6-8.1 (2H), 8.0-7.6 (2H), 7.4-6.5 (18H); MS (70 eV, EI) m/z=518 (M+)

Reference： [1]Patent: US9935272,2018,B2 .Location in patent: Page/Page column 64-65

63
[ 106-39-8 ]
[ 135-67-1 ]
10-(4-chlorophenyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; potassium carbonate; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 110℃; for 4.5h; Inert atmosphere;	3.i In a 50 mL four-necked flask purged with nitrogen, Phenoxazine 1.83 g (10 mmol), 1.92 g (10 mmol) of 1-bromo-4-chlorobenzene, 2.76 g (20 mmol) of potassium carbonate, And 50 mL of toluene, and nitrogen bubbling was carried out for 1 hour. Thereafter, 0.44 g (1.5 mmol) of [(tBu) 3 PH] BF 4, 0.11 g (0.5 mmol) of Pd (OAc) 2 was added, The mixture was heated and stirred at 110 ° C. under a nitrogen atmosphere, The reaction was initiated. After 3.5 hours, it was confirmed by TLC that the raw material phenoxazine was almost consumed, After 1 hour, the reaction was stopped. A peak derived from the objective substance was observed by MS. Thereafter, salt and the like are removed by suction filtration, Two times with 50 mL of water with a separatory funnel, And washed once with 50 mL of saturated saline solution.Dehydrated with sodium sulfate, After removal it was concentrated. 2.9 g of yellow to gray solid was obtained. Purification was then carried out by column chromatography. Since it was one spot on TLC, It was about a withdrawal column. A Φ 4.2 cm column tube was filled with 140 cc of silica gel (about 10 cm high) And the developing solvent (toluene: hexane = 1: 4). Recover spots of the object, And concentrated to obtain 3.0 g of a white solid. After drying in a vacuum dryer, 2.51 g (85% yield) of a white solid was obtained.
85%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;
84.8%	With palladium diacetate; potassium carbonate; tri-tert-butylphosphonium hydrogen tetrafluoroborate In 5,5-dimethyl-1,3-cyclohexadiene; water monomer at 140℃; for 15h; Inert atmosphere;	1.1 Step 1 N2 inlet pipe, thermometer,Into a 200 ml four-necked flask equipped with a reflux tube,1-Bromo-4-chlorobenzene (4.08 g, 21.3 mmol), phenoxazine (3.9 g, 21.3 mmol)Potassium carbonate (K 2 CO 3) (5.86 g, 42.6 mmol) and xylene (130 ml) were charged,After N 2 bubbling for 90 minutes, Pd (OAc) 2 (240 mg, 1.07 mmol) and [(tBu) 3 PH] BF 4 (927 mg, 3.12 mmol) were added and heated to 140 ° C.The mixture was stirred under reflux for 15 hours. after that,H 2 0, toluene and saturated brine,After dehydration with sodium sulfate, concentration.And purified by silica column chromatography (eluent CH 2 Cl 2: hexane = 1: 4).After drying under reduced pressure, 5.3 g (84.8%) of the desired product was obtained.

70%

With tri-tert-butyl phosphine; palladium diacetate; sodium tertiary butoxide In toluene at 110℃; Inert atmosphere;

1 Add 15.7g p-chlorobromobenzene, 15.2g phenoxazine, 0.56gPd(OAc)2, 11.38gt-BuONa and 800mL toluene into a 2L four-neck flask, install heating, stirring, reflux, temperature control and nitrogen protection device, nitrogen After replacing 5 times, use a 25ml syringe to quickly add 19.8gP(t-Bu)3 in 10% toluene solution, heat up at 110 and reflux for 6-8h, sample and detect GC, and the phenoxazine content is less than 0.5% to stop the reaction. Nitrogen protection After cooling to room temperature, after quenching, washing with water, drying, column chromatography, desolventizing, and isopropanol recrystallization, 16.82 g of I-1a-2 was obtained with a yield of 70%.

Reference： [1]Current Patent Assignee: YAMAGATA UNIVERSITY - JP2018/35135, 2018, A Location in patent: Paragraph 0050-0051
[2]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[3]Current Patent Assignee: YAMAGATA UNIVERSITY - JP2018/127426, 2018, A Location in patent: Paragraph 0052; 0053
[4]Current Patent Assignee: SHANDONG SHENGHUA NEW MATERIAL TECHNOLOGY CO LTD - CN111848542, 2020, A Location in patent: Paragraph 0013

64
[ 135-67-1 ]
[ 27012-25-5 ]
10-(6-phenylpyridin-3-yl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tris-(dibenzylideneacetone)dipalladium(0); potassium tert-butylate; XPhos; In toluene; for 24h;Inert atmosphere; Reflux;	To a flask charged with <strong>[27012-25-5]5-bromo-2-phenylpyridine</strong> (2.81 g, 12.0 mmol), phenoxazine (2.00 g, 10.9 mmol), tris(dibenzylideneacetone) dipalladium (200 mg, 0.218 mmol), 2-(dicyclohexylphosphino)-15 246'-trw'-propyl-l,l'-biphenyl (X-PHOS) (312 mg, 0..655 mmol), and potassium t-butoxide (2.45 g, 21.8 mmol) under a N2 atmosphere was added toluene (80 mL) at room temperature. The flask was attached to a reflux condenser and heated to reflux. After 24 h, the crude reaction mixture was cooled to rt, diluted with water, and extracted with ethyl acetate. The organic layer was washed with water and brine, and then dried over MgSCv20 The resulting solution was filtered and concentrated. The resulting residue was purified via silica gel chromatography, eluted with hexane:CH2Cl2 = 1:1, to afford the product as a white solid in 83% yield.

Reference： [1]Patent: KR2018/30860,2018,A .Location in patent: Paragraph 0071-0072

65
[ 135-67-1 ]
[ 1122-91-4 ]
4-(10H-phenoxazin-10-yl)benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene at 110 - 120℃; Inert atmosphere;	1 Synthesis of 1a: Add p-bromobenzaldehyde (183mg, 1.00mmol, 1.0 equivalent) to a dry three-necked flask with a magnetic stirring rotor and condenser.Phenoxazine (220mg, 1.2mmol, 1.2 equivalent),Palladium acetate (7mg, 0.03mmol, 3mol%),Potassium carbonate (415mg, 3.00mmol, 3 equivalents),Then the nitrogen was pumped three times, and tri-tert-butyl phosphine (6.2 mg, 0.08 mmol, 8.0 mol%) and toluene (4 mL) were added under the protection of nitrogen.The mixture was stirred for 12 hours in an oil bath at 120°C.TLC monitors until the reaction of the raw materials is complete, and cool to room temperature.A small amount of water was added and extracted with ethyl acetate.The aqueous layer was extracted twice with ethyl acetate.The organic phases were combined, dried over anhydrous sodium sulfate, and filtered.The solvent was distilled off under reduced pressure.The obtained crude product was separated and purified by silica gel chromatography column, eluent: petroleum ether/ethyl acetate=20:1,Intermediate 1a was obtained, 273 mg of pale yellow solid, with a yield of 95%.
92%	Stage #1: phenoxazine; 4-bromo-benzaldehyde With potassium carbonate In toluene for 0.5h; Inert atmosphere; Stage #2: With palladium diacetate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 12h; Inert atmosphere;	1.3 Synthesis steps of compound 7-1: Weigh 509.0mg of p-bromobenzaldehyde 5-1 and 450.0mg of phenoxazine into a 25mL round bottom flask,Pour 10mL of toluene,Dissolve by ultrasound.Add 1.0005g of K2CO3 to the reaction solution,After blowing nitrogen for 30 minutes, 28.0mg of Pd(OAc)2 and 108.0mg of tBu3PHBF4 were added. Reflux for 12h at 110°C,TLC was used to check the progress of the reaction.After the reaction, the reaction liquid was extracted with water and DCM.The organic phase was dried with anhydrous sodium sulfate for 3 hours and then spin-dried.Get the reaction mixture.The resulting reaction mixture was dissolved with DCM,Separation through the column,The eluent uses a mixed solution of petroleum ether and DCM (volume ratio 4:1) to elute the product,Spin dry the product and dry overnight,658.9 mg of yellow solid 7-1 was obtained,The yield was 92%.
82.6%	With palladium diacetate; caesium carbonate; triphenylphosphine In toluene at 110℃; for 24h; Inert atmosphere;	4-(10H-Phenoxazin-10-yl)benzaldehyde: 4-Bromobenzaldehyde (1.82 g, 9.84 mmol), Pd(OAc)2 (0.11 g, 0.49 mmmol), PPh3 (0.39 g, 1.48 mmol), Cs2CO3 (7.69 g, 23.60 mmol) and 10H-phenoxazine (1.50 g, 8.20 mmol) were dissolved in 100 mL of anhydrous toluene. The reaction mixture was refluxed with stirring for 24 h under a nitrogen atmosphere, and then cooled to room temperature. The resulting mixture was poured into 200 mL of water and extracted with dichloromethane (3 x100 mL). The organic phase was washed with water (2 x 100 mL) and dried over anhydrous Na2SO4. After filtering, the filtrate was evaporated to dryness under reduced pressure. The crude was purified by chromatography on silica gel using ethyl acetate/petroleum ether (1:50, v/v) as the eluent to give 4-(10H-phenoxazin-10-yl)benzaldehyde (yield 82.6%). 1H NMR (600 MHz, CDCl3, δ, ppm): 10.10 (s, 1H), 8.11 (d, J = 8.4 Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 6.73 (d, J = 8.2 Hz, 2H), 6.70 (t, J = 7.2 Hz, 2H), 6.62 (t, J = 7.6 Hz, 2H), 5.97 (d, J = 7.8 Hz, 2H).

Reference： [1]Current Patent Assignee: ZHEJIANG HONGWU TECHNOLOGY CO LTD - CN111662286, 2020, A Location in patent: Paragraph 0049-0051
[2]Current Patent Assignee: HEFEI UNIVERSITY - CN113480551, 2021, A Location in patent: Paragraph 0043; 0053-0056
[3]Yu, Tianzhi; Li, Xinyu; Zhao, Yuling; Yang, Qianguang; Li, Yanmei; Zhang, Hui; Li, Zhaolin [Journal of Photochemistry and Photobiology A: Chemistry, 2018, vol. 360, p. 58 - 63]

66
[ 135-67-1 ]
[ 5407-04-5 ]
[ 23690-11-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: phenoxazine With n-butyllithium In hexane; toluene at -78℃; for 1h; Inert atmosphere; Stage #2: 3-(dimethylamino)propyl chloride hydrochloride With n-butyllithium; triisobutylaluminum In hexane; toluene Reflux; Inert atmosphere;	4.2. Spacer attachment (method A) General procedure: n-BuLi (1.6M in hexane) was added slowly at-78°C under an inert argon atmosphere in dry toluene (70mL) to a solution of the starting amine and stirred for 1h. Then n-BuLi (1.6M in hexane) and triisobutylalumane (TIBA) were added slowly under argon at-78°C to a stirring solution of 2-chloro-N,N-dimethyl-ethanamine hydrochloride (10) or 3-chloro-N,N-dimethyl-propanamine hydrochloride (56) in dry toluene (30mL), stirring continued 1hat-78°C and added slowly to the previously prepared solution of the starting amine; the resulting mixture was refluxed over night. The crude product was obtained after cooling using ice and the product filtered off to remove tetrabutylammonium chloride (TBACl)/TIBA. The residue was extracted with a mixture of ethyl acetate (100mL) and saturated NaHCO3 solution (20mL), the organic phase washed with 10mL brine, dried with anhydrous Na2SO4 and concentrated under reduced pressure to obtain a colored, oily product. Finally the oily product was purified by column chromatography (silica gel 60 (0.063-0.2 mm/70-230 mesh ASTM), chloroform-methanol 10:1 and 5:1 (v/v)).

Reference： [1]Blaess, Markus; Bibak, Nelly; Claus, Ralf A.; Kohl, Matthias; Bonaterra, Gabriel A.; Kinscherf, Ralf; Laufer, Stefan; Deigner, Hans-Peter [European Journal of Medicinal Chemistry, 2018, vol. 153, p. 73 - 104]

67
[ 135-67-1 ]
[ 2050-47-7 ]
C₂₄H₁₆BrNO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); potassium tert-butylate; In toluene; at 110℃; for 10h;Inert atmosphere;	<strong>[2050-47-7]4,4'-dibromodiphenyl ether</strong> in a 100 mL round bottom flask (30 mmol, 9.77 g), phenoxazine (5 mmol, 910 mg), tris(diphenylidene acetonide) dioxime (0.1 mmol, 92 mg), 1,1'-bis(diphenylphosphino)ferrocene (0.2 mmol, 111mg), potassium t-butoxide (10 mmol, 1.12 g) was dissolved in 40 mL of toluene, and the mixture was stirred at 110 C under reflux for 10 hours under nitrogen atmosphere. After the reaction was completed, it was extracted with dichloromethane, and the extract was concentrated by rotary evaporation.Column chromatography (petroleum ether: methylene chloride = 50:1, vol.) gave white solid ( 965mg, yield: 45%).

Reference： [1]Patent: CN108129386,2018,A .Location in patent: Paragraph 0068; 0070; 0071

68
[ 29504-81-2 ]
[ 135-67-1 ]
C₁₆H₁₀BrNOS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In 5,5-dimethyl-1,3-cyclohexadiene; at 105 - 115℃; for 1h;Inert atmosphere;	First, phenoxazine (71.8 g, 360 mmol) and <strong>[29504-81-2]2-bromo-5-iodothiophene</strong> (104 g, 360 mmol) were added to xylene (1.7 liters) in a 3 liter flask under an argon gas flow. The internal temperature was raised to 105 C. TBu3P·HBF4 (4.18 g, 14.4 mmol) and Pd2(dba 3) (6.59 g, 7.20 mmol) were added to the mixture, tBuONa (41.6 g, 433 mmol) was added in portions. Thereafter, the temperature was raised to 115 C. and stirred for 1 hour.After cooling to room temperature, the reaction solution was added to water (1.8 liter), and the organic layer was separated. The organic layer was washed with water (500 ml), separated, and concentrated under reduced pressure. The obtained crude product (107 g) was purified by silica gel column chromatography (2 kg, development: toluene / heptane = 1/2) to obtain the desired product. (Yield 39 g, Yield 30%)

Reference： [1]Patent: JP2018/111673,2018,A .Location in patent: Paragraph 0195; 0200-0203

69
[ 135-67-1 ]
[ 345-83-5 ]
C₂₅H₁₇NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With potassium-t-butoxide In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;
	Stage #1: (10H)-phenoxazine With potassium-t-butoxide for 0.5h; Inert atmosphere; Reflux; Stage #2: (4-fluorophenyl)(phenyl)methanone In N,N-dimethyl-formamide at 110℃; for 12h;	4 Synthesis of Compound A 8.24 mmol of phenoxazine and 15.0 mmol of potassium tert-butoxide may be added to a round-bottom flask, and the round-bottom flask may be filled with Ar gas. The resultant mixture may be stirred under reflux for about 30 minutes by using 20 ml of anhydrous DMF as a solvent. A solution in which 7.49 mmol of 4-fluorobenzophenone is dissolved in 10 ml of anhydrous DMF may be added to the round-bottom flask and stirred under reflux at a temperature of about 110° C. for about 12 hours. Afier the reaction was completed, the reaction solution may be dissolved in water, and an organic material may be extracted therefrom by using methylene chloride and purified by column chromatography to obtain Compound A of a yellow solid phase.

Reference： [1]Chen, Zhanxiang; Gong, Shaolong; Wang, Tao; Yang, Chuluo; Ying, Ao; Zhu, Yingyu [Journal of Materials Chemistry C, 2022, vol. 10, # 13, p. 5065 - 5069]
[2]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung); SEOUL NATIONAL UNIVERSITY - US2018/240982, 2018, A1 Location in patent: Paragraph 0340; 0341

70
[ 135-67-1 ]
[ 16372-96-6 ]
[ 1313412-22-4 ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	1-Phenyl-3,5-dibromobenzene (3.1 g, 10 mmol), phenoxazine (2.0 g, 11 mmol) was added to the reaction flask, sodium t-butoxide (1.2 g, 12 mmol) Pd2 (dba) 3 (0.1 g, 0.1 mmol), 50 ml of toluene was added to the reaction flask in turn, refluxed under nitrogen for 10 hours, cooled to room temperature, 100 ml of water was added, liquid was separated, the aqueous layer was extracted with ethyl acetate, and the organic layers were combined with saturated brine. And washed with water, the organic layer was dried over magnesium sulfate.Filtered, the filtrate was spun dry, passed through a silica gel column,The HPLC purity was 99.3%, and S1 was obtained.

Reference： [1]Patent: CN109206439,2019,A .Location in patent: Paragraph 0056; 0057; 0058; 0059

71
[ 135-67-1 ]
[ 1897-52-5 ]
2,6-di(10H-phenoxazin-10-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium ethanolate In N,N-dimethyl-formamide at 70 - 150℃; for 48h;	2 Example 2: Synthesis of compound 3b: Dissolve 2,6-difluoro-benzonitrile 1a (10.0mmol, 1.39g), phenoxazine 2b (20.0mmol, 3.66g) and sodium ethoxide (30.0mmol, 2.04g) in DMF at 70 to 150°C React for 48 hours, cool to room temperature, wash with water, extract with dichloromethane, dry with anhydrous sodium sulfate, and then column chromatography to obtain 3b (4.51g, yield: 97%);
82%	With sodium hydride In hexane; N,N-dimethyl-formamide; mineral oil for 10h; Inert atmosphere;

Reference： [1]Current Patent Assignee: XINYANG NORMAL UNIVERSITY - CN112110873, 2020, A Location in patent: Paragraph 0045-0048
[2]Kim, Mounggon; Yoon, Seong-Jun; Han, Si Hyun; Ansari, Ramin; Kieffer, John; Lee, Jun Yeob; Kim, Jinsang [Chemistry - A European Journal, 2019, vol. 25, # 7, p. 1829 - 1834]

72
[ 689260-53-5 ]
[ 135-67-1 ]
C₅₀H₃₆BN₃O₂ [ No CAS ]

Reference： [1]Patent: CN109134520,2019,A

73
[ 135-67-1 ]
[ 194416-45-0 ]
C₃₂H₂₆N₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93.2%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 20 - 110℃; for 24h;Inert atmosphere;	(i) Add compound 4 (1.69 g, 4.40 mmol) to a dry reaction vessel,Phenothiazine (0.732 g, 4.00 mmol), catalyst palladium acetate (0.018 g, 0.08 mmol),Tri-tert-butylphosphine (5% mmol), sodium tert-butoxide (0.577 g, 6.00 mmol)And solvent toluene (50mL), under nitrogen protection and stirring at room temperature,It was then heated to 110 C for 24 h. After the reaction is completed, cool to room temperature.50 mL of dichloromethane was added to the reaction solution, and washed three times with 150 mL of water.The organic layer was collected, the solvent was removed under reduced pressure, and the residue was purified by silica gel chromatography.Petroleum ether/dichloromethane (4:1 vol/vol) as eluent, dried under vacuum,Compound 1 (1.618 g, yield: 93.2%) was obtained as white solid.

Reference： [1]Patent: CN109265410,2019,A .Location in patent: Paragraph 0051-0054

74
[ 135-67-1 ]
[ 589-87-7 ]
[ 694-83-7 ]
[ 71041-21-9 ]

Yield	Reaction Conditions	Operation in experiment
67%	With copper(l) iodide; sodium t-butanolate; In 1,4-dioxane; at 110℃; for 6h;Inert atmosphere;	In a dry nitrogen atmosphere, a mixture of phenoxazine (0.92 g, 5 mmol), 1-bromo-4-iodobenzene (1.7 g, 6 mmol), sodium tert-butoxide (1.06 g, 11 mmol), cuprous iodide (0.02 g, 0.11 mmol) and 1, 2-diaminocyclohexane (0.07 g, 0.6 mmol) in 20 ml dry 1, 4-dioxane was heated under 110 C for 6 h. After the reaction, the mixture was cooled to room temperature and quenched with water and extracted with chloroform. The combined organic layer was washed with distilled water three times and dried over anhydrous magnesium sulfate. Then the solvent was evaporated in a vacuum. The crude product was purified by column chromatography on silica gel using petroleum ether/dichloromethane (9/1 v/v) as the eluent to obtain the product as white solid (1.13 g, 67%). 1H NMR (500 MHz, CDCl3) δ (TMS, ppm) 7.75 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 8.5 Hz, 2H), 6.61-6.73 (m, 6H), 5.94 (d, J = 7.8 Hz, 2H). MS (ESI) (mass m/z): 338.3 [M+H]+, C18H12BrNO calc. 338.2.

Reference： [1]Journal of Photochemistry and Photobiology A: Chemistry,2019,vol. 377,p. 67 - 74

75
[ 135-67-1 ]
[ 3029-64-9 ]
C₄₁H₂₄N₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60.3%		6.37 g (35 mmol) of phenoxazine was added to a 250 ml three-necked flask, and 100 ml of N,N-dimethylformamide was added as a reaction solvent, and the mixture was stirred on a magnetic stirrer for 10 min under ice bath. 0.72 g (30 mmol) of NaH was added portionwise to the reaction flask and stirring was continued for 1 h.Dissolve 2.07 g (10 mmol) of <strong>[3029-64-9]2,4,6-trichloro-5-cyanopyrimidine</strong> in 40 mlThe N,N-dimethylformamide solution was added dropwise to the reaction system, and after the addition was completed, the reaction was carried out at room temperature for 24 hours. After the reaction was completed, the reaction solution was poured into 200 ml of 10percent diluted hydrochloric acid, and the mixture was filtered under reduced pressure, washed with water and dried, and the crude product was obtained from petroleum ether and dichloromethane (PE: DCM=10: 1) Pass the column for the mobile phase. 3.91 g of a white solid powder was obtained in a yield of 60.3percent.

Reference： [1]Patent: CN109553606,2019,A .Location in patent: Paragraph 0089; 0090

76
[ 135-67-1 ]
[ 202865-85-8 ]
C₁₉H₁₄BrNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		Phenoxazine (1.83 g, 10 mmol), 2-bromo-5-iodobenzene (1.57 ml, 2.07 g/mL, 11 mmol), cuprous iodide(0.38 g, 0.2 mmol) and sodium tert-butoxide (1.92 g, 20 mmol) were added to the reaction flask, and nitrogen gas was exchanged three times (10 min/time), and the solvent (1,4-dioxane) was injected under a nitrogen atmosphere. After the raw material is partially dissolved, 2 ml of 1,2-diaminocyclohexane (coordinating agent) is injected, and after the completion of the injection, the reaction is refluxed at 110 C for 6 hours, extracted, concentrated, and powdered, and separated and purified by column chromatography to obtain a white solid product. 2, the yield is 65%.

Reference： [1]Patent: CN109593079,2019,A .Location in patent: Paragraph 0077; 0081; 0082; 0083

77
[ 135-67-1 ]
[ 7351-74-8 ]
C₃₄H₂₂N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With tri-tert-butyl phosphine; caesium carbonate; bis(dibenzylideneacetone)-palladium(0); In 1,2-dichloro-benzene; for 24h;Reflux; Inert atmosphere;	858 mg of N-63 (3 mmol), 1.2 g of PXZ-1 (6.6 mmol),6.5g cesium carbonate (19.8mmol),86mg bis (dibenzylideneacetone) palladium (0.15mmol), 30mg of tri-tert-butylphosphine (0.15mmol) and 35mL of o-dichlorobenzene were added to a 100mL double-necked flask, and heated under reflux for 24 hours under the protection of nitrogen,After cooling to room temperature, the reaction solution was filtered, and 100 mL of water was added to the filtrate.Extract the organic phase with 100 mL of dichloromethane,The organic phase was separated and concentrated to 5.5 mLThe target product was obtained by column chromatography using dichloromethane and petroleum ether (volumeC ratio 1: 3) as eluent.Sublimation in vacuo then gave 0.97 g of yellow product 201 (66% yield).

Reference： [1]Patent: CN110386905,2019,A .Location in patent: Paragraph 0106; 0108; 0109; 0110

78
[ 135-67-1 ]
[ 619-44-3 ]
methyl 4-(10H-phenoxazin-10-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium carbonate In N,N-dimethyl-formamide at 220℃; for 6h; Inert atmosphere;	3.1 (1) Preparation of N-(4-methyl formate phenyl)phenoxazine: Take 5mmol phenoxazine,10 mmol of methyl 4-iodobenzoate and 6 mmol of potassium carbonate,Dissolved in 30mL of dry N, N-dimethylformamide,In a nitrogen atmosphere, the mixture was stirred and reacted in an oil bath at 220 ° C for 6 hours.Then cooled to room temperature, poured into dichloromethane, dissolved organic matter with dichloromethane,Then, the inorganic matters were removed by filtration, and column chromatography (wherein the volume ratio of ethyl acetate to n-hexane was 1:10),N- (4-methyl formate phenyl) phenoxazine was obtained as a pale yellow crystalline solid with a yield of 94%;
90%	With copper(I) oxide In N,N-dimethyl acetamide at 160℃; for 24h; Inert atmosphere;	Methyl 4-(10H-phenoxazin-10-yl) benzoate (M1): To a two-necksround-bottom flask, 10H-phenoxazine (3.66 g, 20 mmol), methyl iodobenzoate(5.50 g, 21 mmol), cuprous oxide (6.00 g, 42 mmol) anddimethylacetamide (30 mL) were added. The mixture was stirred at 160C for 24 h under nitrogen atmosphere. After cooling to room temperature,the mixture was filtrated and the filtrate was poured into 500 mLwater and stirred for 10 min. The crude product was collected byfiltration and purified by column chromatography on silica gel (eluent:petroleum/dichloromethane = 1:1) to provide a pale green solid (5.78 g,90% yield). 1H NMR (600 MHz, CDCl3, ): 8.26 (d, J = 8.2 Hz, 2H), 7.44(d, J = 8.2 Hz, 2H), 6.70 (t, J = 5.8 Hz, 2H), 6.67 (t, J = 7.8 Hz, 2H), 6.59(t, J = 7.3 Hz, 2H), 5.92 (d, J = 7.9 Hz, 2H), 3.97 (s, 3H). HRMS:317.1056 [M]+ (calcd: 317.11). Anal. Calcd for C20H15NO3: C 75.70, H4.76, N 4.41, O 15.12; found: C 75.58, H 4.77, N 4.43, O 15.20.
90%	With copper(I) oxide In N,N-dimethyl acetamide at 160℃; for 8h;	1.S1 S1: Synthesis of PHXB-1: Add 3.66g or 20mmol of phenoxazine, 5.24g or 20mmol of methyl p-iodobenzoate, 5.71g or 40mmol of cuprous oxide and 300mL of N,N-dimethylacetamide into a 500mL three-necked flask. After evacuating for five times, the temperature was slowly raised to 160°C, and the reaction was continued for 8 hours before stopping; after cooling to room temperature, the cuprous oxide was filtered out, and 600 mL of deionized water was added to the resulting filtrate to precipitate solids. Petroleum ether (dichloromethane/petroleum ether volume ratio 1:1) 3000 mL was used as the eluent to purify the crude product through column chromatography to obtain a light green solid with a yield of 90%.

Reference： [1]Current Patent Assignee: ZHENGZHOU UNIVERSITY - CN110437172, 2019, A Location in patent: Paragraph 0063-0068
[2]Chen, Jinlei; Chen, Shanyong; Guan, Youwei; Li, Lu; Wang, Peng; Yan, Xingwu; Yu, Hong; Yu, Junsheng [Dyes and Pigments, 2020, vol. 183]
[3]Current Patent Assignee: UNIVERSITY OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA - CN111153892, 2020, A Location in patent: Paragraph 0050-0052

79
[ 135-67-1 ]
[ 13292-05-2 ]
3-(10H-phenoxazin-10-yl)phenanthrene-9,10-dione [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2019,vol. 58,p. 14660 - 14665
Angew. Chem.,2019,vol. 131,p. 14802 - 14807,6

80
[ 135-67-1 ]
[ 194853-86-6 ]
4-phenoxazin-10-yl-2-trifluoromethylbenzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%		General procedure: Sixty per cent NaH in oil was washed with hexane and then added to a stirred solution of phenothiazine 5 or phenoxazine 6 derivative (10.0mmol) in dry THF (15mL) under a nitrogen atmosphere at room temperature. After stirring for 30min, 4-fluoro-2-(fluoromethyl)-benzonitrile 7 was added. (0007) The reaction mixture was quenched with water (30mL). The organic phase was separated, dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The residue obtained was purified by column chromatography using a mixture of hexane/ethyl acetate (3:1) as eluent.

Reference： [1]Dyes and Pigments,2020,vol. 175

81
[ 135-67-1 ]
4-(4-methoxyphenoxy)-7-bromobenzo[c] [1,2,5]thiadiazole [ No CAS ]
10-(7-(4-methoxyphenoxy)benzo[c][1.2.5]thiadiazole-4-yl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 24h; Inert atmosphere; Schlenk technique;	2.4. Synthesis of the aryloxy-BTD derivatives 4a and 4b via Buchwald-Hartwig amination General procedure: An oven-dried screw-capped Schlenk flask was evacuated, back-filled with nitrogen and loaded with 2a (0.32 mmol, 110 mg), phenoxazine oriminodibenzyl (0.48 mmol), Pd(OAc)2 (1.2 10 2 mmol, 2.7 mg, 4 mol%), tri-tert-butylphosphonium tetrafluoroborate (3.6 10 2 mmol, 10.4mg, 12 mol%), sodium tert-butoxide (0.48 mmol, 46.1 mg) and anhydroustoluene (2 mL). The reaction was stirred at 110 °C for 24 h and allowed tocool-down to room temperature. The mixture was diluted with dichloromethane(30 mL) and washed with water. The organic fraction was driedover sodium sulphate. filtrated and concentrated under vacuum. Thecrude product was purified by column chromatography on silica gel usinghexane/ethyl acetate (from 100:1 to 20:1) as mobile phase.

Reference： [1]Aucélio, Ricardo Queiroz; Back, Davi; Carvalho, Rafael dos Santos; Cremona, Marco; Jardim Barreto, Arthur Rodrigues; Limberger, Jones; Maqueira, Luis; Pazini, Alessandra; Rodembusch, Fabiano Severo; Valente, Felipe Miranda; da Silveira Santos, Fabiano [Dyes and Pigments, 2020, vol. 178]

82
[ 135-67-1 ]
[ 171408-84-7 ]
2,7-di(10H-phenoxazin-10-yl)-9,9'-spirobi[fluorene] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene at 110℃; for 12h; Inert atmosphere;	2.3 Ge2.3 General procedure for synthesis of SBF-PXZ and SBF-PTZneral procedure for synthesis of SBF-PXZ and SBF-PTZ The synthetic scheme of SBF-PXZ and SBF-PTZ was depicted in Fig. 1 (a). 2,7-dibromo-9,9′-spirobifluorene (SBF) was purchased from Sigma-Aldrich. A solution of tri-tert-butylphosphine (0.5mL of 1.0M solution, 0.5mmol) in toluene (10mL) was added into a magnetically stirred mixture of 2,7-dibromo-9,9′-spirobifluorene (1.0g, 2.1mmol), 10H-phenoxazine (0.849g, 4.6mmol)/10H- phenothiazine (0.929g, 4.6mmol), palladium(II) acetate (0.031g, 0.14mmol), and potassium carbonate (1.92g, 13.9mmol) in toluene (30mL). The reaction mixture was stirred at 110°C under an N2 atmosphere for 12h. The reaction mixture was cooled and quenched with water, and the product was extracted thrice with chloroform. The combined organic layer was washed with saturated brine, and water. Dried the organic layer over anhydrous sodium sulfate and concentrated in reduced pressure. The obtained crude product was purified by column chromatography by eluting on silica gel using n-hexane and ethyl acetate (9:1) as an eluent. The corresponding purified products were characterized by 1H and 13C NMR spectroscopy, LC-MS, elemental analysis and FT-IR. The results unveiled the structural arrangement and elemental composition of the prepared samples of SBF-PXZ and SBF-PTZ with the following results.2.3.1 2,7-di(10H-phenoxazin-10-yl)-9,9′-spirobi[fluorene] (SBF-PXZ)White solid; Yield: 92%; 1H NMR (400MHz, CDCl3) δ 8.10 (d, J=8.0Hz, 2H), 7.79 (d, J=7.6Hz, 2H), 7.40 (d, J=8.0Hz, 2H), 7.36 (t, J=7.5Hz, 2H), 7.16 (t, J=7.5Hz, 2H), 6.89 (d, J=7.6Hz, 2H), 6.79 (s, 2H), 6.62 (d, J=7.1Hz, 5H), 6.59 (s, 1H), 6.53 (t, J=8.1Hz, 4H), 5.85 (d, J=7.3Hz, 3H); 13C NMR (101MHz, CDCl3) δ 152.61, 147.23, 143.86, 141.80, 140.86, 138.51, 134.12, 130.39, 128.26, 128.05, 126.93, 123.44, 123.13, 122.57, 121.27, 120.37, 115.36, 112.97. LC-MS (ES+1): m/z calculated for C49H30N2O2: 678.23; found: 678.4 with 97.76% purity. Elemental analysis calculated for C49H30N2O2: C, 86.70; H, 4.45; N, 4.13; O, 4.71; found: C, 83.77; H, 4.77; N, 3.96; O, 6.68.

Reference： [1]Hafeez, Hassan; Jesuraj, P. Justin; Kamaraj, Eswaran; Kim, Chang-Su; Kim, Donghyun; Lee, Changmin; Park, Sanghyuk; Ryu, Seung Yoon; Shin, Sung Tae; Somasundaram, Sivaraman; Song, Myungkwan; Won, Sang Hee [Organic electronics, 2020, vol. 85]

83
[ 1072-85-1 ]
[ 135-67-1 ]
[ 131013-62-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24h;	The preparation method of the compound of formula M1 is: In a 250mL two-necked flask, 2.7g (15.0mmol) phenoxazine,10.7g (60.0mmol) 1-bromo-2-fluorobenzene,8.5g (20.0mmol) cesium carbonate and 130mL N,N-dimethylformamide,Stir and heat to 150°C to react for 24 hours.After the reaction is complete, cool the system to room temperature and pour it into water,Vacuum filtration under reduced pressure, and wash the filter residue with a lot of water,The filter residue was separated and purified on a silica gel column with the eluent of dichloromethane: petroleum ether = 1:4 (volume ratio),Obtained 4.6g M1 with a yield of 92.0%.

Reference： [1]Current Patent Assignee: SOOCHOW UNIVERSITY (SUZHOU) - CN111704624, 2020, A Location in patent: Paragraph 0091-0092

84
[ 135-67-1 ]
[ 608-21-9 ]
10,10'-(2-bromo-1,3-phenylene)bis(10H-phenoxazine) [ No CAS ]

Reference： [1]Journal of Materials Chemistry C,2021,vol. 9,p. 8308 - 8313

85
[ 4096-21-3 ]
[ 135-67-1 ]
10-(4-(pyrrolidin-1-yl)phenyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With dipotassium peroxodisulfate In acetonitrile at 20℃; for 1h; regioselective reaction;

Reference： [1]Lei, Aiwen; Wang, Pengjie; Wang, Shengchun; Wang, Xiaoyu; Yi, Hong; Zhang, He; Zhang, Heng [Green Chemistry, 2022, vol. 24, # 1, p. 147 - 151]

86
[ 135-67-1 ]
[ 552-82-9 ]
N-methyl-4-(10H-phenoxazin-10-yl)-N-phenylaniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With dipotassium peroxodisulfate In acetonitrile at 20℃; for 1h; regioselective reaction;

Reference： [1]Lei, Aiwen; Wang, Pengjie; Wang, Shengchun; Wang, Xiaoyu; Yi, Hong; Zhang, He; Zhang, Heng [Green Chemistry, 2022, vol. 24, # 1, p. 147 - 151]

87
[ 135-67-1 ]
[ 100189-84-2 ]
10-(4-bromo-3,5-dimethylphenyl)-10H-phenoxazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; methylmagnesium chloride In toluene at 100℃; for 8h; Inert atmosphere;

Reference： [1]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]

88
[ 135-67-1 ]
[ 128259-71-2 ]
C₃₀H₁₈Br₂N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (10H)-phenoxazine With Cs₂CO₃ In N,N-dimethyl-formamide at 60℃; for 0.25h; Inert atmosphere; Stage #2: 2,5-dibromo-1,3-difluorobenzene In N,N-dimethyl-formamide at 155℃; for 12h; Inert atmosphere;	5.1 1) Synthesis of intermediate (5) First, phenoxazine (8.06 g, 44 mmol), Cs2CO3(32.50 g, 100 mmol) were sequentially added to a 250 mL two-necked round-bottomed flask, and then, under Ar atmosphere, 50 mL of ultra-dry DMF was injected through a syringe , resulting in a suspension, which was stirred at 60°C for 15 minutes.Finally, 5-bromo-2-chloro-1,3-difluorobenzene (5.44 g, 20 mmol) was added at one time from the side opening of the reaction flask, and the temperature was raised to 155° C. for 12 h.After the reaction was completed, it was lowered to room temperature, the insoluble inorganic salt was filtered off, and then the high-boiling DMF solvent was removed by vacuum concentration, and the residue was purified by a column machine, and the optimized eluent formula was DCM/PE (1:5, v/v) to obtain a powder of intermediate (5).

Reference： [1]Current Patent Assignee: SHENZHEN UNIVERSITY - CN113788851, 2021, A Location in patent: Paragraph 0103-0107

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	135-67-1	MDL No. :	MFCD00005014
Formula :	C₁₂H₉NO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	TZMSYXZUNZXBOL-UHFFFAOYSA-N
M.W :	183.21	Pubchem ID :	67278
Synonyms :	NSC 72990	Chemical Name :	10H-Phenoxazine

Num. heavy atoms :	14
Num. arom. heavy atoms :	12
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	1.0
Molar Refractivity :	58.99
TPSA :	21.26 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	Yes
Log Kp (skin permeation) :	-4.68 cm/s

Log Po/w (iLOGP) :	2.14
Log Po/w (XLOGP3) :	3.85
Log Po/w (WLOGP) :	3.16
Log Po/w (MLOGP) :	2.56
Log Po/w (SILICOS-IT) :	2.7
Consensus Log Po/w :	2.88

[ CAS No. 135-67-1 ] {[proInfo.proName]}

Quality Control of [ 135-67-1 ]

Related Doc. of [ 135-67-1 ]

Product Details of [ 135-67-1 ]

Calculated chemistry of [ 135-67-1 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 135-67-1 ]

Application In Synthesis of [ 135-67-1 ]

[ 135-67-1 ] Synthesis Path-Downstream 1~88

Related Parent Nucleus of
[ 135-67-1 ]

Other Aromatic Heterocycles

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

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

Log S (ESOL) :	-4.04
Solubility :	0.0169 mg/ml ; 0.0000921 mol/l
Class :	Moderately soluble
Log S (Ali) :	-3.99
Solubility :	0.0186 mg/ml ; 0.000102 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-4.7
Solubility :	0.00366 mg/ml ; 0.00002 mol/l
Class :	Moderately soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	2.62

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

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P378
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P391	Collect spillage. Hazardous to the aquatic environment
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