Name: 67492-50-6|3,5-Dichlorophenylboronic acid|97%
Brand: Ambeed
SKU: A205014
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1
[ 67492-50-6 ]
[ 200049-46-3 ]
7-(3,5-Dichloro-phenyl)-2,3-dihydro-isoindol-1-one [ No CAS ]

Reference： [1]Heterocycles,1997,vol. 45,p. 2217 - 2221

2
[ 60633-25-2 ]
[ 67492-50-6 ]
3',5,5'-trichloro-2-methoxybiphenyl [ No CAS ]

Reference： [1]Chemosphere,2001,vol. 45,p. 1119 - 1127

3
[ 50638-47-6 ]
[ 67492-50-6 ]
3,3',5-trichloro-4-methoxybiphenyl [ No CAS ]

Reference： [1]Chemosphere,2002,vol. 46,p. 485 - 488

4
[ 153034-94-7 ]
[ 67492-50-6 ]
[ 777096-60-3 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 4603 - 4606

5
[ 67492-50-6 ]
[ 360575-29-7 ]
[ 861218-27-1 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2005,vol. 15,p. 2998 - 3001

6
(R)-2-iodo-2'-(methoxymethoxy)-1,1'-binaphthyl [ No CAS ]
[ 67492-50-6 ]
2-(3,5-dichloro-phenyl)-2'-methoxymethoxy-[1,1']binaphthalenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 14h;Heating / reflux;	(Synthesis Example 5 of Complex); (aR)-3-Formyl-2'-(3,5-dichloro-4-trimethylsilylphenyl)-2-hydroxy-1,1'-binaphtyl is synthesized according to the following reaction scheme 2. [Show Image] Concretely, the compound represented by the above formula (XXXV) [which is synthesized according to the method described in K. Omura, T. Uchida, R. Irie, and T.Katsuki, Chem. Commun., 2060-2061(2004)] (194mg, 0.44mmol) is dissolved in toluene (3.5 mL) under nitrogen at room temperature, and added with <strong>[67492-50-6]3,5-dichlorobenzeneboronic acid</strong> (232 mg, 0.88 mmol, 2 eq), aqueous sodium carbonate (1 mol/L, 3.5 mL) and tetrakis(triphenylphosphine)palladium (25.5 mg, 22 mumol, 5 molpercent). The resulting solution is refluxed for 14 hours and then extracted with ethyl acetate. The ethyl acetate phase is washed with saturated saline, dried with anhydrous sodium sulfate and then concentrated under a reduced pressure. The residue thus obtained is separated through a chromatography with silica gel (hexane/ethyl acetate=30/1) to obtain the compound represented by the above formula (XXXVI) in a yield of 92percent. Results of the 1H-NMR (400 MHz, CDCl3, 25 °C) to the compound of the formula (XXXVI) thus obtained are delta8.02(d, J=8.5Hz, 1H), 7.96(d, J=8.3Hz, 1H), 7.86(d, J=9.0Hz, 1H), 7.80(d, J=8.3Hz, 1H), 7.58(d, J=8.5Hz, 1H), 7.49(m, 2H), 7.26(m, 4H), 7.06(d, J=1.7Hz, 2H), 7.00(m, 2H), 5.04(d, J=7.1Hz, 1H), 4.96(d, J=7.1Hz, 1H) and 3.18(s, 3H).

Reference： [1]Tetrahedron Letters,2006,vol. 47,p. 1571 - 1574
[2]Patent: EP1767524,2007,A1 .Location in patent: Page/Page column 17-18

7
[ 67492-50-6 ]
[ 33284-52-5 ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium acetate; silver(l) oxide; In methanol; at 40℃; for 20h;	General procedure: A mixture of arylboronic acid 3 (0.2 mmol), nano-Pd (0.1molpercent Pd), Ag2O (45 molpercent), KOAc (1 equiv), and CH3OH (0.8mL) was stirred at 40 oC until complete consumption of starting materialas judged by TLC. After the mixture was filtered and evaporated, the residue was purified by flash column chromatography to afford the corresponding homocoupling product 4 (petroleum ether or petroleum ether/ethyl acetate).

Reference： [1]Tetrahedron,2016,vol. 72,p. 6996 - 7002
[2]European Journal of Organic Chemistry,2009,p. 1864 - 1867
[3]Synlett,2007,p. 1913 - 1916

8
[ 1564-64-3 ]
[ 67492-50-6 ]
[ 1213241-18-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 7h;Heating / reflux;	[51.1] Into a three-necked flask, 3,5-dichlorobenzene-1-boronic acid (3.0 g), 9-bromoanthracene (4.47 g) and Pd(PPh3)4 (0.54 g) were placed, and the system was purged with argon. To the resultant mixture, toluene (20 ml) and an aqueous solution (2.4 ml) of sodium carbonate (5.02 g) were added, and the obtained mixture was heated under the refluxing condition for 7 hours. The reaction solution was treated by extraction with toluene, and the extract was concentrated under a reduced pressure. The obtained solid was washed with ethanol, and Compound 1 was obtained (the amount of the product: 4.52 g; the yield: 89percent). 1H-NMR (CDCl3): delta (ppm) 8.51 (s,1H), 8.2-8.0 (m, 2H), 7.8-7.0 (m. 9H)

Reference： [1]Patent: EP1440959,2004,A1 .Location in patent: Page 23

9
[ 864086-51-1 ]
[ 67492-50-6 ]
7-(3,5-dichlorophenyl)-5H-dibenzo[c,g]chromene-3,9-diol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In DMF (N,N-dimethyl-formamide); water; at 120℃; for 1h;	Example 45; 7- (3, 5-Dichlorophenyl)-5H-dibenzo [c, g] chromene-3, 9-diol [0089]; To a mixture of 7-bromo-H-dibenzo [c, g] chromene-3,9-diol (343 mg, 1 mmol), dimethylformamide (5 mL), 2 M sodium carbonate (1 mL), water (1 mL), and tetrakis (triphenylphosphine) palladium (116 mg, 0.1 mmol) was added 3,5-difluoro- phenylboronic acid (573 mg, 3 mmol). The reaction mixture was heated to 120 °C for 1 hr, then cooled and diluted with ethyl acetate (25 mL) and 5percent ammonium chloride. The organic layer was washed with water (3 x 10 mL) and brine (10 mL) and dried over anhydrous magnesium sulfate. The solvent was removed and the resulting dark liquid was purified by chromatography (2.5percent acetonitrile-dichloromethane) to afford a tan solid (178.9 mg, 44percent): mp 252-255 °C ; lH NMR (DMSO-d6) : No. 5.01 (2H, s), 6.57 (1H, d, J=2. 3 Hz), 6.64 (1H, d, J=2. 4 Hz), 6.84 (1H, dd, J=2. 5 Hz, J=8. 5 Hz), 6.94 (1H, dd, J=2. 3 Hz, J=8.8 Hz), 7.42 (2H, d, J=1. 9 Hz), 7.66-7. 70 (1 H, m), 7.79-7. 85 (2H, m), 8.25 (1H, s), 9.68 (1H, s), 9.76 (1H, s); MS m/z 409/411/413,2 Cl ([M+H] +). An. HPLC gave purity of 97.6percent 280 nm. Anal. for C23Hl4C1203 : Calc'd: C: 67.50 ; H: 3.45 Found: C: 67.13 ; H: 3.63

Reference： [1]Patent: WO2005/82880,2005,A1 .Location in patent: Page/Page column 40-41

10
[ 91062-61-2 ]
[ 67492-50-6 ]
5-(3,5-dichlorophenyl)-1H-indole-2-carboxylic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With sodium carbonate;palladium diacetate; triphenylphosphine; In isopropyl alcohol; acetonitrile; for 3h;Heating / reflux;	To a stirred solution of 5-bromo-3-chloro-1H-indole-2-carboxylic acid ethyl ester (500 mg, 1.86 mmol) and <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (530 mg, 2.78 mmol) in a mixture of MeCN (26 mL) and i-PrOH (3.3 mL) at room temperature under argon, was added Pd(OAc)2 (12 mg, 0.05 mmol), Ph3P (40 mg, 0.15 mmol) and Na2CO3 (2M aq. , 16 mL) and the resulting mixture was heated at reflux for 3 h. After cooling to room temperature the reaction was diluted with water (20 mL) and extracted with EtOAc (3x30 mL). The combined organic extracts were washed with water, brine and dried (MgS04). Solvent removal and purification by chromatography afforded . the sub-title compound (430 mg, 69percent).

Reference： [1]Patent: WO2005/123673,2005,A1 .Location in patent: Page/Page column 91

11
[ 849677-13-0 ]
[ 67492-50-6 ]
[ 849677-14-1 ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; for 8h;Heating / reflux;	Into a three neck flask, Intermediate Product 2-2 (1.65 g, 3.3 mmol), <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (0.63 g, 3.3 mmol) and Pd(PPh3)4 (0.20 g, 0.17 mmol) were placed and the atmosphere in the flask was replaced with argon gas. Dimethylformamide (10 milliliter) and an aqueous solution (5 milliliter) of potassium carbonate (1.38 g, 10.0 mmol) were added to the resultant solution and then, it was refluxed under heating for 8 hours. The resultant reaction solution was extracted by toluene, followed by vacuum concentration. The obtained solid thereafter was refined with silica gel column chromatography (dissolution solvent: methylene chloride) and as a result, Intermediate Product 2-3 was obtained. Produced Amount: 1.51 g, Yield: 81 percent

Reference： [1]Patent: EP1659129,2006,A1 .Location in patent: Page/Page column 94-95

12
[ 21440-97-1 ]
[ 67492-50-6 ]
[ 304854-14-6 ]

Yield	Reaction Conditions	Operation in experiment
		EXAMPLE 61 6-(3,5-dichloro-phenyl)4,4-dimethyl-1,4-dihydrobenzo-[d][1,3]oxazin-2-one Prepared from 6-bromo-4,4-dimethyl-1,4-dihydro-benzo[d] [1,3]oxazin-2-one and 3,5-dichlorophenyl boronic acid according to Procedure A. A white solid: mp 245-246 C.; 1H-NMR (DMSO-d6) delta10.4 (s, 1H), 7.77 (m, 2H), 7.67-7.64 (m, 2H), 7.56 (bs, 1H), 6.96 (d, 1H, J=7.98 Hz), 1.7 (s, 6H); MS (EI) m/z 321 ([M+H]+, 40%); Anal. Calc. For C16H13Cl2NO2: C, 59.32, H, 4.11, N, 4.32. Found: C, 59.13, H, 4.29 N, 4.17.
		EXAMPLE 61 6-(3,5dichloro-phenyl)-4,4-dimethyl-1,4-dihydrobenzo-[d][1,3]oxazin-2-one Prepared from <strong>[21440-97-1]6-bromo-4,4-dimethyl-1,4-dihydro-benzo[d][1,3]oxazin-2-one</strong> and 3,5-dichlorophenyl boronic acid according to Procedure A. A white solid: mp 245-246 C.; 1H-NMR (DMSO-d6) delta10.4 (s, 1H), 7.77 (m, 2H), 7.67-7.64 (m, 2H), 7.56 (bs, 1H), 6.96 (d, 1H, J=7.98 Hz), 1.7 (s, 6H); MS (EI) m/z 321 ([M+H]+, 40%); Anal. Calc. For C16H13Cl2NO2: C, 59.32, H, 4.11, N, 4.32. Found: C, 59.13, H, 4.29, N, 4.17.

Reference： [1]Patent: US2002/49204,2002,A1
[2]Patent: US6444668,2002,B1

13
[ 5419-55-6 ]
[ 3032-81-3 ]
[ 67492-50-6 ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium;	Step A Synthesis of 3,5-dichlorophenylboronic acid as an intermediate This compound was prepared in a manner analogous to that of Step C of Example 2, using 20.0 grams (0.073 mole) of <strong>[3032-81-3]3,5-dichlorophenyl iodide</strong>, 32.0 mL of n-butyllithium (0.080 mole--2.5M in hexanes) and 48.6 mL (0.220 mole) of triisopropyl borate. The yield of 3,5-dichlorophenyl-boronic acid was 6.7 grams; mp >250° C. The NMR spectrum was consistent with the proposed structure.

Reference： [1]Patent: US5534518,1996,A

14
[ 1514-82-5 ]
[ 67492-50-6 ]
[ 864725-22-4 ]

Yield	Reaction Conditions	Operation in experiment
97.8%	With potassium carbonate;(1,4-naphthoquinone)-[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(0); In 1,4-dioxane; water; at 90℃; for 5h;Inert atmosphere;Product distribution / selectivity;	5 g (26.2 mmol) of 3,5-dichlorophenylboronic acid and 6.87 g (39.3 mmol) of 2-bromo-3,3,3-trifluoropropene were dissolved in 25 g of 1,4-dioxane and to the resultant solution, 10 g of water, 7.24 g (52.4 mmol) of potassium carbonate and 9.2 mg (0.013 mmol as palladium) of 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0) dimer were added, followed by heating to reflux at 90° C. in a nitrogen atmosphere for 5 hours. After the reaction completion, the product was cooled and to the mixture, 10 g of water and 20 g of ethyl acetate were added. The phases were separated and to the organic phase, 10 g of a saturated salt solution were added to separate the phases again. The solvent was distilled off under reduced pressure and the residue was purified by a distillation under reduced pressure to obtain 6.18 g of a fraction of 58 to 64° C./2 mmHg. This fraction was a colorless liquid of 2-(3,5-dichlorophenyl)-3,3,3-trifluoropropene. Yield: 97.8percent.1H NMR (CDCl3, Me4Si, 300 MHz) delta 7.40 (t, J=2.0 Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (m, 1H), 5.83 (m, 1H).
85%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In tetrahydrofuran; water; at 70℃; for 4h;Sealed tube;	Step 7: Preparation of 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene A mixture of 3,5-dichlorophenylboronic acid (5 g, 26.2 mmol), 2-bromo-3,3,3-trifluoroprop-1-ene (5 g, 28.6 mmol), K2CO3 (7.24 g, 52.4 mmol) and Pd(PPh3)2Cl2 (368 mg) in THF (20 mL) and H2O (10 mL) was heated at 70° C. in a sealed tube for 4 h. The mixture was cooled to rt and partitioned between ether (50 mL) and H2O (50 mL). The aqueous layer was extracted with ether (50 mL) and the combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography over silica gel eluted with hexanes to afford 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene (5.77 g; yield 85percent) as a white solid. 1H NMR (400 MHz, CDCl3): delta 7.42 (t, J=2.0 Hz, 2H), 7.34 (d, J=2.0 Hz, 1H), 6.05 (s, 1H), 5.82 (s, 1H) ppm.
83%	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; at 0 - 90℃; for 6h;Sealed tube;	Step 4: Preparation of 1 ,3-dichloro-5-(1-trifluoromethyl-vinyl)-benzene; 3,5-Dichlorophenylboronic acid (25.0 g, 13.1 mmol) was dissolved in THF/H2O (200 mL:50 mL) in a sealed tube. Potassium carbonate (37.8 g, 273 mmol) was added and the solution was cooled to 0 0C. 2-Bromo-3,3,3-trifluoroprop-1-ene (20.1 mL, 155 mmol) and dichlorobis(triphenylphosphine) palladium(ll) (1.83 g, 2.62 mmol) were added and the solution was heated to 90 0C for 6 h. The mixture was cooled to room temperature, diluted with 4 ethyl acetate (250 mL), and then filtered through a bed of celite. The organic layer was washed with water (200 mL) and brine (200 ml_). The combined organic layers were dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica-gel column chromatography. A gummy white gel-like substance was obtained. Upon addition of MTBE (methyl-tert- butyl ether), a white solid precipitated which was removed by filtration; the filtrate was concentrated to afford the title compound (26.0 g, 83percent) as a yellow oil.1H-NMR (400 MHz, CDCI3) delta = 7.40 (d, J = 2.0 Hz, 1 H), 7.34 (d, J = 1.6 Hz, 2H), 6.05 (d, J = 1.2 Hz, 1 H), 5.83 (d, J = 1.6 Hz, 1 H).

80%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In tetrahydrofuran; at 70℃; for 4h;Sealed tube;	Step 11: Preparation of 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene A mixture of 3,5-dichlorophenylboronic acid (3.8 g, 20.0 mmol), 2-bromo-3,3,3-trifluoro-prop-1-ene (4.9 g, 28 mmol), Cs2CO3 (20 mL, 2 M, 40 mmol) and Pd(PPh3)2Cl2 (421 mg) in THF (30 mL) was heated at 70° C. in a sealed tube for 4 h. The mixture was cooled to rt and partitioned between ether and H2O. The aqueous layer was extracted with EA and the combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography over silica gel eluted with hexanes to give 1,3-dichloro-5-(3,3,3-trifluoroprop-1-en-2-yl)benzene (3.85 g; yield 80percent). 1H NMR (500 MHz, CDCl3): delta 7.41 (s, 1H), 7.35 (s, 2H), 6.06 (s, 1H), 5.83 (s, 1H) ppm.
80%	With bis(triphenylphosphine)palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 0 - 90℃; for 6h;Sealed tube;	3,5-Dichlorophenylboronic acid (1 eq), potassium carbonate (2 eq) and dichlorobis- (triphenylphosphine)palladium(ll) (0.015 eq) were placed in a pressure tube. A mixture of THF/H20 (2: 1) was added and the tube was sealed with septum. After being degassed for 10min with nitrogen the reaction mixture was cooled down to 0 °C and 2-Bromo-3,3,3- trifluoroprop-1-ene (1.2 eq) was added via syringe. Next the solution was heated to 90 °C for 6 h, cooled down to room temperature and diluted with ethyl acetate. After separation, the organic layer was washed with water and brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure till dryness. BB1 (R=CI) was purified by means of silica-gel column chromatography using 100percent cyclohexane as mobile phase to deliver the title product in 80percent yield as a white gel-like substance. LCMS gave no ionization.
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; for 3h;Heating / reflux;	In a solution of 25.0 g of 3,5-dichlorophenyl boric acid in 200 ml of tetrahydrofuran and 100 ml of water, 27.5 g of 2-bromo-3,3,3-trifluoropropene, 38.0 g of potassium carbonate and 1.84 g of dichlorobis(triphenylphosphine) palladium (II) were added, and stirred under reflux with heat for 3 hours. After the completion of the reaction and cooling to room temperature, 500 ml of ice water was added, and extracted with ethyl acetate (500 ml x 1). The organic phase was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was purified with silica gel column chromatography that was eluated with hexane, and 25.7 g of the aimed product was obtained as colorless oily substance. 1H NMR (CDCl3, Me4Si, 300MHz) delta7.41 (t, J=2.0Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (q, J=3.2Hz, 1H), 5.82 (q, J=3.2Hz, 1 H).
	With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,2-dimethoxyethane; water; at 75℃; for 3h;	Step C : Preparation of l,3-dichloro-5-[l-(trifluoromethyl)ethenyl]ben2ene; To a mixture of tetrahydrofuran (33 mL), ethylene glycol dimethyl ether (33 mL), and 4 N aqueous potassium hydroxide (33 mL) in a 200 mL Fisher-Porter sealed tube was added <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (8.72 g, 45.7 mmol) and 2-bromo-3,3,3-trifluoro- propene (10.0 g, 57.2 mmol), followed by the addition of tetrakis(triphenylphosphine)palladim (0) (264 mg, 0.229 mmol). The mixture was heated to 75 0C for 3 h. The reaction mixture was then partitioned between diethyl ether and water. <n="29"/>The aqueous layer was extracted with diethyl ether (2 x 20 mL). The organic extracts were combined, dried (MgSO^, and concentrated under reduced pressure to provide a residue. The residue was purified by silica gel chromatography to afford the title compound as a clear oil (4.421 g). lH NMR (CDCl3): delta 7.41 (s, 2H), 7.33 (s, IH), 6.04 (d, IH), 5.82 (d, IH).
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; for 3h;Reflux;	To a solution of 25.0 g of 3,5-dichlorophenylboric acid in 200 mL of tetrahydrofuran and 100 mL of water, 27.5 g of 2-bromo-3,3,3-trifluoropropene, 38.0 g of potassium carbonate and 1.84 g of dichloro-bis(triphenylphosphine) palladium (II) were added and the resultant mixture was stirred while heating the mixture to reflux for 3 hours. After the completion of the reaction, the reaction mixture was left to be cooled to room temperature and 500 mL of ice water was added to the mixture, followed by extracting the mixture with ethyl acetate (500 mL.x.1). The organic phase was cleaned with water and then dried over anhydrous sodium sulfate, and the solvent was distilled off from the organic phase under reduced pressure, followed by purifying the resultant residue by silica gel column chromatography eluting with hexane to obtain 25.7 g of the objective substance as a colorless oily substance. 1H NMR (CDCl3, Me4Si, 300 MHz) delta 7.41 (t, J=2.0 Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (q, J=3.2 Hz, 1H), 5.82 (q, J=3.2 Hz, 1H)
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; for 3h;Reflux;	Process 1; Production of 3,5-dichloro-1-(1-trifluoromethylethenyl) benzene To a solution of 25.0 g of <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> in 200 mL of tetrahydrofuran and 100 mL of water, 27.5 g of 2-bromo-3,3,3-trifluoropropene, 38.0 g of potassium carbonate and 1.84 g of dichlorobis(triphenylphosphine) palladium (II) were added, and the resultant reaction mixture was stirred while heating the mixture to reflux for 3 hours. After the completion of the reaction, the reaction mixture was left to be cooled down to room temperature and 500 mL of ice water was added to the reaction mixture, followed by extracting the reaction mixture with ethyl acetate (500 mL.x.1). Subsequently, the organic phase was washed with water and was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resultant residue was purified by silica gel column chromatography eluting with hexane to obtain 25.7 g of the objective substance as a colorless oily substance. 1H NMR (CDCl3, Me4Si, 400 MHz) delta 7.41 (t, J=2.0 Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (q, J=3.2 Hz, 1H), 5.82 (q, J=3.2 Hz, 1H).
	With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,2-dimethoxyethane; water; at 75℃; for 3h;	To a mixture of tetrahydrofuran (33 mL), 1,2-dimethoxyethane (33 mL), and 4 N aqueous potassium hydroxide (33 mL) in a 200 mL Fisher-Porter sealed tube was added 3,5- dichlorophenylboronic acid (8.72 g, 45.7 mmol) and 2-bromo-3,3,3-trifluoropropene (10.0 g, 57.2 mmol), followed by the addition of tetrakis(triphenylphosphine)palladium (0) (264 mg, 0.229 mmol). Then the mixture was heated to 75 0C for 3 h. The reaction mixture was partitioned between diethyl ether and water. The aqueous extract was washed with diethyl ether (2 x 20 mL). The organic extracts were combined, dried (MgSO4), and concentrated under reduced pressure. The residue was purified by silica gel chromatography using hexanes/ethyl acetate as eluent to afford the title compound as a clear oil (4.421 g). 1H NMR (CDCl3): delta 7.41 (s, 2H), 7.33 (s, IH), 6.04 (d, IH), 5.82 (d, IH).
	With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,2-dimethoxyethane; water; at 75℃; for 3h;Sealed tube;	Example 1; Preparation of 5-(3,5-dichlorophenyl)-4,5-dihydro-3-[4-(1H-pyrazol-1-yl)phenyl]-5-(trifluoromethyl)isoxazoleStep A: Preparation of 1,3-dichloro-5-[1-(trifluoromethyl)ethenyl]benzeneTo a mixture of tetrahydrofuran (33 mL), ethylene glycol dimethyl ether (33 mL), and 4 N aqueous potassium hydroxide (33 mL) in a 200 mL Fisher-Porter sealed tube was added 3,5-dichlorophenylboronic acid (8.72 g, 45.7 mmol) and 2-bromo-3,3,3-trifluoro-propene (10.0 g, 57.2 mmol), followed by the addition of tetrakis(triphenylphosphine)-palladium(0) (264 mg, 0.229 mmol). The mixture was heated to 75° C. for 3 h. Then the reaction mixture was partitioned between diethyl ether and water. The aqueous extract was washed with diethyl ether (2.x.20 mL). The organic extracts were combined, dried (MgSO4), and concentrated under reduced pressure to provide a residue. The residue was purified by silica gel chromatography and eluted with hexane to afford 4.421 g of the title compound as a clear oil.1H NMR (CDCl3) delta 7.41 (s, 2H), 7.33 (s, 1H), 6.04 (d, 1H), 5.82 (d, 1H).
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; for 3h;Heating / reflux;	Step 1: Production of of 3,5-dichloro-1-(1-trifluoromethylethenyl)benzene In a solution of 25.0 g of 3,5-dichlorophenyl boric acid in 200 mL of tetrahydrofuran and 100 mL of water, 27.5 g of 2-bromo-3,3,3-trifluoropropene, 38.0 g of potassium carbonate and 1.84 g of dichlorobis(triphenylphosphine) palladium (II) were added, and stirred under reflux with heat for 3 hours. After the completion of the reaction, the reaction mixture was left and cooled to room temperature, 500 mL of ice water was added, and extracted with ethyl acetate (500 mL x 1). The organic phase was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was purified with silica gel column chromatography that was eluated with hexane to obtain 25.7 g of the aimed product as colorless oily substance. 1H NMR (CDCl3, Me4Si, 300MHz) delta7.41 (t, J=2.0Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (q, J=3.2Hz, 1 H), 5.82 (q, J=3.2Hz, 1 H).
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; water; for 3h;Heating / reflux;	Step 1: Production of of 3,5-dichloro-1-(1-trifluoromethylethenyl)benzene In a solution of 25.0 g of 3,5-dichlorophenyl boric acid in 200 mL of tetrahydrofuran and 100 mL of water, 27.5 g of 2-bromo-3,3,3-trifluoropropene, 38.0 g of potassium carbonate and 1.84 g of dichlorobis(triphenylphosphine) palladium (II) were added, and stirred under reflux with heat for 3 hours. After the completion of the reaction, the reaction mixture was left and cooled to room temperature, 500 mL of ice water was added, and extracted with ethyl acetate (500 mL x 1). The organic phase was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was purified with silica gel column chromatography that was eluated with hexane to obtain 25.7 g of the aimed product as colorless oily substance. 1H NMR (CDCl3, Me4Si, 300MHz) delta7.41 (t, J=2.0Hz, 1H), 7.3-7.35 (m, 2H), 6.05 (q, J=3.2Hz, 1 H), 5.82 (q, J=3.2Hz, 1 H).
	With potassium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; 1,2-dimethoxyethane; water; at 75℃; for 3h;	Step B: Preparation of l,3-dichloro-5-[l-(trifluoromethyl)ethenyl]benzene; To a mixture of tetrahydrofuran (33 mL), ethylene glycol dimethyl ether (33 mL), and aqueous potassium hydroxide (4 N, 33 mL) in a 200 mL Fisher-Porter sealed tube was added 3,5-dichlorophenylboronic acid (8.72 g, 45.7 mmol) and 2-bromo-3,3,3-trifluoropropene (10.0 g, 57.2 mmol), followed by the addition of tetrakis(triphenylphosphine)palladium(0) (264 mg, 0.23 mmol). The mixture was heated to 75 0C for 3 h. The reaction mixture was partitioned between diethyl ether and water. The aqueous extract was extracted with diethyl ether (2 x 20 mL). The organic extracts were combined, dried (MgSC^), and concentrated <n="33"/>under reduced pressure to provide a residue. The residue was purified by chromatography on silica gel using 10percent ethyl acetate/hexanes as eluent to afford the title compound as a clear oil (4.42 g). 1H NMR (CDCl3): delta 7.41 (s, 2H), 7.33 (s, IH), 6.04 (d, IH), 5.82 (d, IH).
25.7 g	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; for 3h;Reflux;	2-bromo-3,3,3-trifluoropropene 27.5 g, potassium carbonate 38.0 g and dichlorobis (triphenylphosphine) in 200 ml tetrahydrofuran and 200 ml solution of 25.0 g 3,5-dichlorophenyl boric acid 1.84 g of palladium (II) was added and stirred for 3 hours under heating reflux. After completion of the reaction, the reaction solution was allowed to cool to room temperature, 500 ml of ice water was added, and extracted with ethyl acetate (500 ml × 1). The organic layer is washed with water, dried over anhydrous sodium sulfate, evaporated under reduced pressure, and the residue is purified by silica gel column chromatography eluting with hexane.25.7 g of the desired product was obtained as a colorless oil.

Reference： [1]Patent: US2010/160683,2010,A1 .Location in patent: Page/Page column 9
[2]Patent: US2013/131016,2013,A1 .Location in patent: Paragraph 0205
[3]Patent: WO2010/112545,2010,A1 .Location in patent: Page/Page column 137-138
[4]Patent: US2013/131017,2013,A1 .Location in patent: Paragraph 0414
[5]Patent: WO2015/132592,2015,A1 .Location in patent: Paragraph 00114
[6]Patent: EP1731512,2006,A1 .Location in patent: Page/Page column 237-238
[7]Patent: WO2007/70606,2007,A2 .Location in patent: Page/Page column 27-28
[8]Patent: EP2151437,2010,A1 .Location in patent: Page/Page column 89
[9]Patent: EP2230230,2010,A1 .Location in patent: Page/Page column 115
[10]Patent: WO2007/79162,2007,A1 .Location in patent: Page/Page column 29
[11]Patent: US7897630,2011,B2 .Location in patent: Page/Page column 35-36
[12]Patent: EP1932836,2008,A1 .Location in patent: Page/Page column 380
[13]Patent: EP1997813,2008,A1 .Location in patent: Page/Page column 203
[14]Patent: WO2007/123855,2007,A2 .Location in patent: Page/Page column 31-32
[15]Patent: JP2019/48883,2019,A .Location in patent: Paragraph 0267; 0268

15
[ 107346-32-7 ]
[ 67492-50-6 ]
4-amino-8-(3,5-dichloro-phenyl)-N-propyl-cinnoline-3-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52.5%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 20℃; for 2 - 24h;Heating / reflux;	Method B: To a solution of the cinnoline-halide in 1,2-dimethoxyethane (10 mL/mmol cinnoline-halide) under nitrogen at ambient temperature was added tetrakis(triphenylphosphine)palladium (0) (0.05-0.15 molar equivalents). After stirring 10-20 min an arylboronic acid, heteroaryl boronic acid, or a boron compound 1-2B of Scheme 2 (1-4 molar equivalents) was added followed by a solution of sodium carbonate (2.5 molar equivalents) in water (3 mL/mmol halide). The resulting mixture was heated at reflux for 2-24 h. The reaction was then cooled to ambient temperature and extracted with ethyl acetate. The residue from the organic extracts was purified by flash chromatography on silica gel eluting with increasingly polar gradient of ethyl acetate in hexanes to afford the desired compound.EXAMPLE 13 4-amino-8-(3,5-dichlorophenyl)-N-propyl-cinnoline-3-carboxamide Using method B, 4-amino-8-bromo-N-propyl-cinnoline-3-carboxamide (100 mg, 0.33 mmol) and <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (252 mg, 1.32 mmol) were reacted to afford the title compound (65 mg, 52.5percent yield) as a pale-yellow solid. 1H NMR (300 MHz, DMSO-d6) delta 9.26 (br, 1H), 8.48 (d, J=8.2 Hz, 1H), 7.95 (d, J=7.2 Hz, 2H), 7.74-7.85 (m, 3H), 7.67 (t, J=2.0 Hz, 1H), 3.31 (m, overlapped with H2O), 1.60 (m, J=7.3 Hz, 2H), 0.91 (t, J=7.4 Hz, 3H). MS APCI, m/z=375/377 (M+H). HPLC 2.52 min.
52.5%		EXAMPLE 13 4-amino-8-(3,5-dichlorophenyl)-N-propyl-cinnoline-3-carboxamide Using method B, 4-amino-8-bromo-N-propyl-cinnoline-3-carboxamide (100 mg, 0.33 mmol) and <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (252 mg, 1.32 mmol) were reacted to afford the title compound (65 mg, 52.5percent yield) as a pale-yellow solid. 1H NMR (300 MHz, DMSO-d6) delta 9.26 (br, 1H), 8.48 (d, J=8.2 Hz, 1H), 7.95 (d, J=7.2 Hz, 2H), 7.74-7.85 (m, 3H), 7.67 (t, J=2.0 Hz, 1H), 3.31 (m, overlapped with H2O), 1.60 (m, J=7.3 Hz, 2H), 0.91 (t, J=7.4 Hz, 3H). MS APCI, m/z=375/377 (M+H). HPLC 2.52 min.

Reference： [1]Patent: US2007/142328,2007,A1 .Location in patent: Page/Page column 28; 87; 89
[2]Patent: US2008/318925,2008,A1

16
[ 70120-14-8 ]
[ 67492-50-6 ]
[ 895131-89-2 ]

Yield	Reaction Conditions	Operation in experiment
25%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 6h;	To a degassed mixture of 6 (0.10 g, 0.33 mmol) in toluene (2 mL) and aqueous 2 M sodium carbonate (Na2CO3) (1 mL), palladium(tetrakis)triphenylphosphine (0.0115 g, 0.033 mmol, 0.1 equiv.) was added, followed by a solution of <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (0.0699 g, 0.363 mmol, 1.1 equiv.) in ethanol (EtOH) (0.5 mL). The reaction was stirred at 80° C. for 6 h. To the reaction mixture, EtOAc (10 mL) was added, and then washed with saturated brine (10 mL), dried (MgSO4), and concentrated to afford the crude product as a black residue. Flashtube.(TM). chromatography was used to purify the crude product, eluding with 20percent EtOAc/cyclohexane. Sections of the Flashtube.(TM). 2008 were cut at the desired bands using the Flashtube.(TM). Cutter (FTC). The section of silica was extracted in EtOAc, filtered off and the solvent evaporated in vacuo. The product was crystallized, and recrystallized thereafter using isopropanol and distilled water. This afforded VSB28 as brown crystals (30 mg, 0.0822 mmol, 25percent): 1H NMR (CDCl3) delta 7.42-7.41 (d, 2H), 7.34-7.33 (d, J=3, 1H), 7.16-7.14 (d, J=6, 1H), 6.98-6.94 (dd, J=3, J2=3, 1H), 6.89-6.88 (d, J=3, 1H), 4.89 (bs, 1H), 1.61-1.56 (m, 2H), 1.29 (s, 6H), 1.26-1.21 (d, 6H), 1.11-1.08 (m, 2H), 0.87-0.83 (t, 3H); 13C NMR (CDCl3) delta 152.26 (C, Ar), 151.90 (C, Ar), 140.92 (C, Ar), 135.26 (CH, Ar), 129.70 (CH, Ar), 127.58 (CH, Ar), 127.28 (CH, Ar), 122.62 (C, Ar), 119.03 (CH, Ar), 114.04 (CH, Ar), 44.46 (CH2), 31.76 (CH2), 29.99 (CH2), 28.84 (CH3), 24.67 (CH2), 22.64 (CH2), 14.03 (CH3); MS (ESP-) m/z 363 (M-1).

Reference： [1]Patent: US2008/262011,2008,A1 .Location in patent: Page/Page column 15-16

17
[ 1029592-85-5 ]
[ 67492-50-6 ]
8-cyclopropyl-8-(3',5'-dichlorobiphenyl-3-yl)-2,3,4,8-tetrahydroimidazo[1,5-a]pyrimidin-6-amine acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
23%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In tetrahydrofuran; water; at 130℃; for 0.5h;Microwave irradiation;	Example 6; delta-Cvclopropyl-delta-CS'^'-dichlorobiphenyl-S-vD^^^^-tetrahvdroimidazorLS-alphalpyrimidialpha- 6-amine acetate; <n="40"/>8-(3-Bromophenyl)-8-cyclopropyl-2,3,4,8-tetrahydroimidazo[l,5-alpha]pyrimidin-6-amine (80 nag, 0.23 mmol), [l,r-bis(diphenylphosphino)ferrocene]palladium(II) chloride dichloromethane adduct (19 mg, 0.023 mmol), cesium carbonate (300 mg, 0.92 mmol), and <strong>[67492-50-6]3,5-dichlorobenzeneboronic acid</strong> (53 mg, 0.35 mmol) was dissolved in tetrahydrofuran: water (9:1) (3 mL) and heated at 130 0C for 30 min in a microwave. When cooled to ambient temperature the mixture was filtered and purified by preparative HPLC to give 24 mg (23percent yield) of the title compound: 1H NMR (DMSO- J6) delta 7.94 - 7.92 (m, 1 H), 7.79 - 7.76 (m, 1 H), 7.65 - 7.63 (m, 2 H), 7.61 - 7.56 (m, 2 H), 7.41 (t, J= 7.78 Hz, 1 H), 3.53 - 3.48 (m, 4 H), 1.88 (s, 3 H, acetate), 1.65 (t, J= 5.65 Hz, 2 H), 1.56 - 1.49 (m, 1 H), 0.43 - 0.36 (m, 1 H), 0.33 - 0.26 (m, 3 H); MS (ESI) m/z 399, 401 [M+l]+.

Reference： [1]Patent: WO2008/63114,2008,A1 .Location in patent: Page/Page column 38-39

18
[ 1035267-25-4 ]
[ 67492-50-6 ]
[ 1035267-30-1 ]

Yield	Reaction Conditions	Operation in experiment
22%	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In tetrahydrofuran; at 130℃; for 2h;Irradiation in a microwave;	4-[2-Aniino-4-(3-bromo-4-fluorophenyl)-l-e1iiyl-5-oxo-4,5-dihydro-lH"-iinidazol-4- yljphenyl methanesulfonate (0.1 g, 0.21 mmol), <strong>[67492-50-6](3,5-dichlorophenyl)boronic acid</strong> (52 mg, 0.27 mmol), [l,r-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (15 mg, 0.021 mmol), potassium carbonate (174 mg, 1.26 mmol), and anhydrous tefrahydrofuran (3 mL) was irradiated in a microwave at 130 °C for 2 h. When cooled to room temperature the mixture was filtered and dimethyl sulfoxide (500 muL) was added. The solution was concentrated in vacuo to remove the tetrahydrofuran and purified by preparative etaPLC to give 25 mg (22percent yield) of the title compound: 1H NMR (CDCl3) delta 7.55 - 7.48 (m, 4H) 7.39 (t, J= 1.5 Hz, 2 H), 7.34 (t, J= 1.9 Hz, 1 H), 7.25 - 7.20 (m, 2 H), 7.11 (dd, J= 10.0, 8.5 Hz, 1 H), 5.44 (br s, 2 H), 3.64 - 3.54 (m, 2 H), 3.12 (s, 3 H), 1.25 (t, J= 7.2 Hz, 3 H); MS (ES) m/z 535.87, 537.89 [M+lf.

Reference： [1]Patent: WO2008/76046,2008,A1 .Location in patent: Page/Page column 164

19
[ 3740-92-9 ]
[ 67492-50-6 ]
[ 1097652-86-2 ]

Reference： [1]Chemical Communications,2008,p. 5821 - 5823

20
[ 1203586-96-2 ]
[ 67492-50-6 ]
[ 1203586-97-3 ]

Yield	Reaction Conditions	Operation in experiment
87%	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; potassium hydroxide;chlorobis(ethylene)rhodium(I) dimer; In 1,4-dioxane; water; at 50℃; for 0.666667h;Inert atmosphere;	A solution of mu-dichlorotetraethylenedirhodium(I) (20 mg, 0.05 mmol, 5 mol percent Rh) and racemic BINAP (69 mg, 0.11 mmol, 5.5 mol percent) in 1,4-dioxane (5 mL) was stirred for 15 min at room temperature under nitrogen. KOH (1.01 mL, 1.01 mmol, 1.0 M aqueous) was added, and the resulting solution was stirred for 6 min at room temperature. After addition of 3,5-dichlorophenylboronic acid (1.16 g, 6.01 mmol) and stirring for 6 min, this mixture was transferred to a Schlenk-flask containing 1-(3,4-dimethoxybenzyl)maleimide (500 mg, 2.02 mmol) in 1,4-dioxane (5 mL) under nitrogen. The resulting mixture was stirred at 50° C. for 40 min. After cooling to RT, the crude reaction mixture was concentrated. Purification by silica gel chromatography (20-60percent ethyl acetate in hexanes) afforded the product as a yellow-white solid (690 mg, 87percent). 1H-NMR (400 MHz, DMSO-d6) delta 7.56 (t, J=1.9 Hz, 1H), 7.44 (d, J=1.8 Hz, 2H), 6.89 (d, J=8.2 Hz, 1H), 6.85 (d, J=1.9 Hz, 1H), 6.81 (dd, J=1.9, 8.2 Hz, 1H), 4.54 (s, 2H), 4.33 (dd, J=5.6, 9.4 Hz, 1H), 3.74 (s, 3H), 3.72 (s, 3H), 3.20 (dd, J=9.4, 18.0 Hz, 1H), 2.91-2.99 (m, 1H). LC/MS (10percent-99percent CH3CN (0.035percent TFA)/H2O (0.05percent TFA), m/z: M+1 obs=394.1; tR=1.81 min.

Reference： [1]Patent: US2010/4300,2010,A1 .Location in patent: Page/Page column 15

21
[ 557-21-1 ]
[ 67492-50-6 ]
[ 6575-00-4 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 11389 - 11391

22
[ 624-28-2 ]
[ 67492-50-6 ]
[ 1259901-33-1 ]

Yield	Reaction Conditions	Operation in experiment
71.9%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 17h;Inert atmosphere;	30.0 g (126.6 mmol) of 2,5-dibromopyridine, 24.6 g (129.1 mmol) of 3,5-dichlorophenylboric acid, 300 ml of toluene, 150 ml of ethanol, 130 ml of 2M sodium carbonate aqueous solution, and 7.3 g (6.33 mmol) of Pd(PPh3)4 were prepared and reacted in a nitrogen atmosphere for 17 hours. Chloroform and water were poured into a reactor vessel and a chloroform layer was fractioned. The chloroform layer was washed with water twice. Its crude material obtained by collecting chloroform was purified with a silica gel column using a developing solvent of chloroform / n-hexane mixture solvent. Structure identification was performed by way of MS and 1H-NMR, and it was confirmed that it was a target. Its yield was 27.6 g (71.9percent yields).

Reference： [1]Patent: EP2275409,2011,A1 .Location in patent: Page/Page column 37

23
[ 15862-18-7 ]
[ 67492-50-6 ]
[ 1259901-17-1 ]

Yield	Reaction Conditions	Operation in experiment
75.6%	With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; water; toluene; for 2h;Inert atmosphere;	9.4 g (29.95 mmol) of 5,5'-dibromo2,2'-bipyridine synthesized by a known method (see J. Org. Chem., 67, p.443 (2002)), 20 g (29.95 mmol) of 3,5-dichlorophenylboric acid, 376 ml of toluene, 188 ml of ethanol, 66 ml of 2M sodium carbonate aqueous solution, and 2.1 g (2.995 mmol) of Pd(PPh3)2Cl2 were prepared and reacted in a nitrogen atmosphere for 2 hours. The precipitated crystal was filtered and washed with water and methanol. The filtrate was separated and a toluene layer was fractioned. The toluene layer was washed with water twice. After washing, a crude material obtained by collecting toluene was mixed with the filtered precipitate crystal. This crude material was subjected to a silica gel process, and the resulting crude material was recrystalized from dimethylacetamide and purified. Structure identification was performed by way of mass spectrometry (MS) and 1H-NMR, and it was confirmed that it was a target. Its yield was 10.1 g (75.6percent yields).

Reference： [1]Patent: EP2275409,2011,A1 .Location in patent: Page/Page column 35

24
[ 412344-70-8 ]
[ 67492-50-6 ]
[ 1259901-26-2 ]

Yield	Reaction Conditions	Operation in experiment
82.3%	With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; water; toluene; for 11.5h;Inert atmosphere;	9.4 g (29.95 mmol) of 5,5'-dibromo2,2'-bipyridine synthesized by a known method (see J. Org. Chem., 67, p.443 (2002)), 20 g (29.95 mmol) of 3,5-dichlorophenylboric acid, 376 ml of toluene, 188 ml of ethanol, 66 ml of 2M sodium carbonate aqueous solution, and 2.1 g (2.995 mmol) of Pd(PPh3)2Cl2 were prepared and reacted in a nitrogen atmosphere for 2 hours. The precipitated crystal was filtered and washed with water and methanol. The filtrate was separated and a toluene layer was fractioned. The toluene layer was washed with water twice. After washing, a crude material obtained by collecting toluene was mixed with the filtered precipitate crystal. This crude material was subjected to a silica gel process, and the resulting crude material was recrystalized from dimethylacetamide and purified. Structure identification was performed by way of mass spectrometry (MS) and 1H-NMR, and it was confirmed that it was a target. Its yield was 10.1 g (75.6percent yields).

Reference： [1]Patent: EP2275409,2011,A1 .Location in patent: Page/Page column 36

25
[ 3430-18-0 ]
[ 67492-50-6 ]
[ 1259901-43-3 ]

Yield	Reaction Conditions	Operation in experiment
56.5%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 73℃; for 28.5h;Inert atmosphere;	25.0 g (99.6 mmol) of 2,5-dibromo-3-picoline, 24.0 g (101.6 mmol) of 3,5-dichlorophenylboric acid, 288 ml of toluene, 144 ml of ethanol, 102 ml of 2M sodium carbonate aqueous solution, and 4.0 g (3.46 mmol) of Pd(PPh3)4 were prepared and reacted in a nitrogen atmosphere for 28.5 hours at 73 °C. Chloroform and water were poured into a reactor vessel, and a chloroform layer was fractioned. The chloroform layer was washed with water twice. A crude material obtained by collecting chloroform was purified with a silica gel column using a developing solvent of chloroform / n-hexane mixture solvent. Structure identification was performed by way of MS and 1H-NMR, and it was confirmed that it was a target. Its yield was 17.9 g (56.5percent yields).

Reference： [1]Patent: EP2275409,2011,A1 .Location in patent: Page/Page column 39

26
[ 1313043-12-7 ]
[ 67492-50-6 ]
[ 1313043-66-1 ]

Yield	Reaction Conditions	Operation in experiment
85%	With caesium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; water; at 80℃;	A. N-(3-{1 -[4-(3,5-Dichloro-phenyl)-1 -(2-methoxy-ethyl)-1 H-indole-3-carbonyl]- piperidin-4-yl}-4-fluoro-benzyl)-2,2,2-trifluoro-acetamideA mixture of N-(3-{1 -[4-bromo-1 -(2-methoxy-ethyl)-1 H-indole-3-carbonyl]- piperidin-4-yl}-4-fluoro-benzyl)-2,2,2-trifluoro-acetamide (200 mg, 0.34 mmol), 3,5- dichlorophenyllboronic acid (78 mg, 0.41 mmol), cesium carbonate (223 mg, 0.68 mmol), and Pd(dppf)CI2.CH2CI2 (28 mg, 10percent mol) in dioxane/H2O (10mL/1 ml_) is heated at 80 °C overnight. The reaction mixture is cooled to r.t, and then filtered through Celite. The filtrate is partitioned between EtOAc and 10percent citric acid. The two layers are separated, and the aqueous layer is extracted with EtOAc once. The combined organic layers are washed with H2O, and brine, dried over Na2SO4, filtered, and concentrated in vacuo. The crude material is purified on silica gel with CH2CI2/MeOH (100/0 to 98/2) as eluent to give the product (190 mg, 85percent) as a beige foam.1 H NMR (300 MHz, CDCI3) delta 7.60-6.90 (m, 10H), 6.53 (br s, 1 H), 4.80-4.60 (m, 1 H), 4.55-4.45 (m, 2H), 4.40-4.30 (m, 2H), 3.80-3.70 (m, 2H), 3.70-3.35 (m, 1 H), 3.34 (s, 3H), 3.00-2.75 (m, 1 H), 2.75-2.05 (m, 2H), 1 .95-1 .00 (m, 4H);LC Rt 1 .17 min; MS 650 (M+H, 100percent).

Reference： [1]Patent: WO2011/79102,2011,A1 .Location in patent: Page/Page column 230-231

27
[ 1208356-32-4 ]
[ 67492-50-6 ]
[ 1208348-70-2 ]

Yield	Reaction Conditions	Operation in experiment
29%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 85℃; for 9h;Inert atmosphere;	Ethyl 4-[4-(3,5-dichlorophenyl)-3-trifluoromethylpyrazol-1-yl]-2-trifluoromethylbenzoate(I-A-Q4-001) 3,5-Dichlorophenylboronic acid (0.60 g, 3.14 mmol) and sodium carbonate (0.69 g, 6.48 mmol) in water (2 ml) are added to a solution of ethyl 4-(4-iodo-3-trifluoromethylpyrazol-1-yl)-2-trifluoromethylbenzoate (1.00 g, 2.09 mmol) in DME (10 ml). The reaction vessel is degassed and filled with nitrogen. Tetrakis(triphenylphosphine)palladium (0.73 g, 0.63 mmol) is added, and the reaction mixture is stirred at 85° C. for 9 h. After cooling, the mixture is poured into water and extracted with ethyl acetate. The organic phase is washed with water and saturated sodium chloride solution, dried over magnesium sulphate and concentrated using a rotary evaporator. Purification by chromatography on silica gel gives ethyl 4-[4-(3,5-dichlorophenyl)-3-trifluoromethylpyrazol-1-yl]-2-trifluoromethylbenzoate (0.30 g, 0.60 mmol, 29percent).1H NMR (CDCl3): 1.42 (t, 3H, J=7.1 Hz), 4.44 (q, 2H, J=7.1 Hz), 7.37-7.42 (m, 3H), 8.00-8.01 (m, 2H), 8.14-8.15 (m, 2H)

Reference： [1]Patent: US2011/190365,2011,A1 .Location in patent: Page/Page column 31-32

28
trifluoromethanesulfonic acid diphenyl(trifluoromethyl)sulfonium salt [ No CAS ]
[ 67492-50-6 ]
[ 54773-20-5 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 9516 - 9518

29
[ 1220904-07-3 ]
[ 67492-50-6 ]
[ 1220904-08-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 110℃;Capped vial;	Step 1; The bromide was prepared according to the Scheme I (Steps 1 -5) using the requisite amino acid, amine, and ketone.To a 20 mL vial was added bromide (100 mg, 0.15 mmoi), Pd(PPh3) (18 mg, 0.10 equiv.), boronic acid (45 mg, 1 .5 equiv.) and 0.5 mL of aq. NaHC03 solution, followed by 5 mL of toluene/EtOH (1/1 ). The via. was capped, sealed, and heated at 1 10 °C overnight. The mixture was cooled to RT and diluted with ether and filtered through Ce.ite.(R). and concentrated. The residue was purified via gradient flash chromatography (ISCO, 0 - 50 percent EtOAc in hexanes, Si02) which furnished the desired compound (100 mg, 92percent yield).

Reference： [1]Patent: WO2011/119559,2011,A1 .Location in patent: Page/Page column 158

30
[ 1021019-74-8 ]
[ 67492-50-6 ]
[ 1353511-58-6 ]

Yield	Reaction Conditions	Operation in experiment
35%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 100℃; for 0.75h;Inert atmosphere; Sealed vessel;	To a 10 mL vial with a magnetic stir bar was added triflate 5 (400 mg, 1.5 mmol), 3,5-dichlorophenylboronic acid (344 mg, 1.8 mmol), Na2CO3 (382 mg, 3.6 mmol) and Pd(PPh3)4 (5percent mol, 87 mg) in a mixture 1,4-dioxane-water (4 mL, 2:1). The vial was sealed and purged with argon through the septum inlet for 5 min. The suspension was then heated at 100 °C for 45 min. After cooling, the resulting mixture was diluted with EtOAc, filtered through Celite and washed with EtOAc. Water was added and the organic layer was extracted twice with EtOAc. The combined organic layers were washed with water, dried over Na2SO4, filtered and concentrated under vacuum. The crude product was purified by silica gel chromatography using petroleum ether/EtOAc (9:1) as eluent. Trituration with diisopropylic ether afforded 2-(3,5-dichlorophenyl)imidazo[1,2-a]pyridine 2c as a white powder (138 mg, 35percent yield). Mp 142-143 °C; 1H NMR (400 MHz, DMSO-d6) delta 8.63 (s, 1 H), 8.57 (d, J = 6.8 Hz, 1 H), 8.04 (d, J = 2.0 Hz, 2 H), 7.63 (d, J = 8.6 Hz, 1 H), 7.58 (t, J = 2.0 Hz, 1 H), 7.33 (ddd, J = 8.6 Hz, J = 7.2 Hz, J = 1.2 Hz, 1 H), 6.97 (ddd, J = 7.2 Hz, J = 6.8 Hz, J = 1.2 Hz, 1 H); 13C NMR (100 MHz, DMSO-d6)delta 144.88, 141.38, 137.51, 134.54, 127.13, 126.79, 125.68, 123.88, 116.83, 112.78, 110.81; IR (KBr) delta 3483, 3375, 2924, 1723, 1600, 1370, 1282, 1252, 1126, 1098, 800, 754 cm-1; MS (ESI) m/z (percent): 263.0 (100) [M+H]+, 265.0 (88) [M+H+2]+, 267.0 (16) [M+H+4]+; Anal. Calcd for C13H8Cl2N2: C 59.34; H 3.06; N 10.65. Found: C 58.96; H 3.12; N 10.25.
35%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 100℃; for 0.75h;Inert atmosphere;	Com-pound was obtained following the representative procedure, using 3,5-dichlorophenylboronic acid (344 mg, 1.8 mmol, 1.2 equiv) and heating for 45 min. The crude product was purified by silica gel chromatography using petroleum ether/ethyl acetate (9/1) as eluent to afford 2-(3,5-dichlorophenyl)imidazo[1,2-a]pyridine 10 as a white powder (138 mg, 35percent yield). Rf = 0.64 (petroleum ether/EtOAc: 7/3); Mp = 142-143 °C. 1H NMR (400 MHz, DMSO-d6): delta 8.63 (s, 1H, H3), 8.57 (d, 1H, 3J = 6.8 Hz, H5), 8.04 (d, 2H, 4J = 2.0 Hz, Ha), 7.64 (d, 1H, 3J = 8.6 Hz, H8), 7.58 (t, 1H, 4J = 2.0 Hz, Hb), 7.33 (ddd, 1H, 3J = 8.6 Hz, 3J = 7.2 Hz, 4J = 1.2 Hz, H7), 6.97 (ddd, 1H, 3J = 7.2 Hz, 3J = 6.8 Hz, 4J = 1.2 Hz, H6). 13C NMR (100 MHz, DMSO-d6): delta 145.09 (C), 141.59 (C), 137.72 (C), 134.75 (2C-Cl), 127.34 (C5), 127.00 (Cb), 125.89 (C7), 124.09 (2Ca), 117.04 (C8), 112.99 (C6), 111.02 (C3). IR (KBr) cm-1: 3071 (nuC-Har), 1600, 1574 (nuC=C and nuC=N), 800, 754 (nuC-Cl). MS (ESI) m/z (percent): 263.0 (100) [M + H]+, 265.0 (88) [M + H + 2]+, 267.0 (16) [M + H + 4]+. Anal. Calcd for C13H8Cl2N2: C, 59.34; H, 3.06; N, 10.65. Found: C, 58.96; H, 3.22; N, 11.02.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 297 - 300
[2]European Journal of Medicinal Chemistry,2012,vol. 58,p. 543 - 556

31
[ 1352420-57-5 ]
[ 67492-50-6 ]
5-[2-(3,5-dichlorophenyl)pyridin-4-yl]-6-fluoro-5-methyl-5,6-dihydro-2H-1,4-oxazin-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
33%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 80℃; for 2h;Inert atmosphere;	Intermediate 157 (0.073 g, 0.212 mmol), 3,5-dichlorophenylboronic acid (0.082 g, 0.425 mmol) and tetrakis(triphenylphosphine) palladium(O) (0.024 g, 0.021 mmol) were dissolved in a mixture of 1 ,4-dioxane (4 mL) and aqueous NaHC03 (sat. sol, 2 mL). The resulting mixture was flushed with N2 and then heated at 80 °C for 2 hours. The reaction mixture was then diluted with water and then extracted with DCM. The combined organic layer were washed with brine, dried (MgS04), filtered and the solvents evaporated in vacuo. . The crude product was dissolved in DCM (5 mL) and TFA (0.8 mL) was added. The mixture was stirred at room temperature for 2 h. The solvents were evaporated in vacuo. The crude product was purified by flash column chromatography (silica gel; methanol/DCM 0/100 to 10/90). The desired fractions were collected and concentrated in vacuo to yield an oil, which was crystallized in DIPE as an off-white solid (0.025 g, 33percent yield).This racemic mixture of diastereomers was then purified by preparative SFC on Chiralpak Diacel Omicron-Eta5muMu (20 x 250 mm), mobile phase (C02, iPrOH with 0.2percent iPrNH2), the desired fractions were collected and evaporated yielding compound 278 (0.0074 g, 10percent yield), compound 277 (0.008 g, 11percent yield) and compound 279(0.0072 g, 9.6percent yield).

Reference： [1]Patent: WO2011/154431,2011,A1 .Location in patent: Page/Page column 125-126

32
[ 1352419-09-0 ]
[ 67492-50-6 ]
[ 1352415-43-0 ]

Yield	Reaction Conditions	Operation in experiment
14%	With potassium phosphate;trans-diacetylpalladium(II) bis(dicyclohexylamine); In ethanol; at 80℃; for 3h;	EtOH (5 mL) was added to a suspension of intermediate 9 (0.25 g, 0.65 mmol), trans- (bisdicyclohexylamine)palladium diacetate [DAPCy, CAS 628339-96-8] (0.038 g, 0.065 mmol), potassium phosphate (0.69 g, 3.26 mmol) and 2,3-dichlorophenylboronic acid (0.19 g, 0.98 mmol). The mixture was stirred at 80 °C for 3 hours. After cooling the mixture was diluted with water and extracted with DCM. The organic layer was separated, dried (Na2S04), filtered and the solvents evaporated in vacuo. The crude product was purified by flash column chromatography (silica gel; 7 M solution of ammonia in methanol / DCM 0/100 to 3/97). The desired fractions were collected and concentrated in vacuo and the residue was purified by preparative HPLC (CI 8 XBridge 19 x 100 5 urn), mobile phase (gradient from 80percent 0.1percent NH4C03H/NH4OH pH 9 solution in Water, 20percent CH3CN to 0percent 0.1percent NH4C03H/NH4OH pH 9 solution in Water, 100percent) CH3CN) , and re-purified under other mobile phase conditions (gradient from 80percent 0.1percent NH4C02CH3 solution in Water, 20percent CH3CN to 0percent 0.1percent NH4C02CH3 solution in Water, 100percent CH3CN) to give compound 2 (0.031 g, 14percent yield) as a solid.

Reference： [1]Patent: WO2011/154431,2011,A1 .Location in patent: Page/Page column 110

33
[ 67492-50-6 ]
[ 57103-20-5 ]
[ 1350856-49-3 ]

Reference： [1]Dyes and Pigments,2012,vol. 92,p. 891 - 896

34
[ 67492-50-6 ]
[ 4373-60-8 ]
[ 1395102-51-8 ]

Reference： [1]Organic electronics,2011,vol. 12,p. 2103 - 2110

35
[ 1383985-05-4 ]
[ 67492-50-6 ]
[ 1383982-40-8 ]

Yield	Reaction Conditions	Operation in experiment
14%	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 100 - 130℃;Inert atmosphere; Sealed vial; Microwave irradiation;	Example 16-(3,5-Dichlorophenyl)-5'-methylspiro[chroman-4,2'-imidazol]-4'-amine; 6-Bromo-5'-methylspiro[chroman-4,2'-imidazol]-4'-amine (73 mg, 0.25 mmol, Intermediate 4), 3,5-dichlorophenylboronic acid (95 mg, 0.50 mmol) and K2CO3 (83 mg, 0.60 mmol) were mixed in dioxane (2 mL) and degassed by passing nitrogen through for 5 min. Then (1,1'-bis(diphenyl-phosphino)ferrocene)-dichloropalladium(II) (10 mg, 0.01 mmol) was added and the mixture was heated in a sealed vial at 100° C. overnight. (1,1'-Bis(diphenylphosphino)ferrocene)-dichloro-palladium(II) (10 mg, 0.01 mmol) was added and heating continued in a microwave oven at 130° C. for 2.x.1 h. Purification by preparative HPLC gave the title compound (13 mg, 14percent yield): 1H NMR (400 MHz, CDCl3) delta ppm 2.04-2.30 (m, 2H), 2.38 (s, 3H), 4.50-4.69 (m, 2H), 4.88 (br s, 2H), 6.69 (s, 1H), 6.98 (d, 1H), 7.22-7.35 (m, 4H); MS (ES+) m/z 360 [M+H]1.

Reference： [1]Patent: US2012/165347,2012,A1 .Location in patent: Page/Page column 45

36
[ 1383743-04-1 ]
[ 67492-50-6 ]
[ 1383741-28-3 ]

Yield	Reaction Conditions	Operation in experiment
50%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; ethanol; at 60℃; for 18h;Inert atmosphere;	Tetrakis(triphenylphosphine)palladium(0) (0.028 g, 0.025 mmol) was added to a stirred suspension of (R)-6-(3-bromo-phenyl)-6-methyl-5,6-dihydro-imidazo[l,2-a]pyrazin-8- ylamine (0.15 g, 0.5 mmol), 3,5-dichlorophenylboronic acid (0.11 g, 0.6 mmol) and potassium carbonate (0.20 g, 1.5 mmol) in 1,4-dioxane (4 mL) and ethanol (0.4 mL) at room temperature under nitrogen. The mixture was stirred at 60 °C for 18 h. The mixture was diluted with water and extracted with DCM. The organic layer was separated, dried (MgS04), filtered and the solvent was evaporated in vacuo. The crude product was purified by flash column chromatography (silica gel; 7 M solution of ammonia in MeOH in DCM 0/100 to 3/97 and then EtOAc/MeOH 0/100 to 10/90). The desired fractions were collected and concentrated in vacuo to yield (R)- 6-(3',5'- dichloro-biphenyl-3-yl)-6-methyl-5,6-dihydro-imidazo[l,2-a]pyrazin-8-ylamine (0.92 g, 50percent yield) as a white solid.

Reference： [1]Patent: WO2012/85038,2012,A1 .Location in patent: Page/Page column 85

37
[ 1383742-41-3 ]
[ 67492-50-6 ]
[ 1383741-26-1 ]

Yield	Reaction Conditions	Operation in experiment
61%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; ethanol; at 60℃; for 18h;Inert atmosphere;	Tetrakis(triphenylphosphine)palladium(0) (0.029 g, 0.025 mmol) was added to a stirred suspension of rac- 6-(3-bromo-phenyl)-6-methyl-5,6-dihydro-imidazo[l,2-a]pyrazin-8- ylamine (0.15 g, 0.5 mmol), 3,5-dichlorophenylboronic acid (0.11 g, 0.6 mmol) and potassium carbonate (0.21 g, 1.5 mmol) in 1,4-dioxane (4 mL) and ethanol (0.4 mL) at room temperature under nitrogen. The mixture was stirred at 60 °C for 18 h. Then the mixture was diluted with water and extracted with DCM. The organic layer was separated, dried (MgS04), filtered and the solvent was evaporated in vacuo. The crude product was purified by flash column chromatography (silica gel; 7 M solution of ammonia in MeOH in DCM 0/100 to 3/97 and then EtOAc/MeOH 0/100 to 10/90). The desired fractions were collected and concentrated in vacuo to yield rac- 6-(3',5'- dichloro-biphenyl-3-yl)-6-methyl-5,6-dihydro-imidazo[l,2-a]pyrazin-8-ylamine (0.114 g, 61percent yield) as a white solid.

Reference： [1]Patent: WO2012/85038,2012,A1 .Location in patent: Page/Page column 85

38
[ 1398113-09-1 ]
[ 76-05-1 ]
[ 67492-50-6 ]
[ 1398112-65-6 ]

Yield	Reaction Conditions	Operation in experiment
70%		Pd(PPh3)4 (30.4 mg, 0.026 mmol) was added to a stirred suspension of intermediate A18 (160 mg, 0.526 mmol), 2,3-dichlorophenyl-boronic acid (120.4 mg, 0.631 mmol) and K2CO3 (218 mg, 1.58 mmol) in a mixture of 1,4-dioxane (4 mL) and EtOH (0.4 mL) in a sealed tube. The mixture was heated at 60 °C for 18 hours. After cooling to room temperature, the mixture was diluted with H20 and NH4C1 (aq. sat. solution) and extracted with DCM. The organic layer was separated, dried (Na2SC>4), filtered and the solvents were evaporated in vacuo. The crude product was purified by short column chromatography (MeOH in DCM 0/100 to 3/97). The desired fractions were collected and concentrated in vacuo to give a solid that was triturated with DIPE, filtered and dried in vacuo at 50 °C to yield compound 2 (136 mg, 70percent yield) as a solid. XH NMR (500 MHz, CDC13) delta ppm 1.56 (s, 3 H), 4.11 (br. s, 2 H), 4.05 (d, J=12.4 Hz, 1 H), 4.10 (d, J=12.7 Hz, 1 H), 6.18 (dd, J=3.8, 2.6 Hz, 1 H), 6.43 (dd, J=3.8, 1.4 Hz, 1 H), 6.75 (dd, J=2.3, 1.4 Hz, 1 H), 7.32 (t, J=1.7 Hz, 1 H), 7.36 - 7.42 (m, 2 H), 7.43 (d, J=1.7 Hz, 2 H), 7.53 (dt, J=6.9, 1.9 Hz, 1 H), 7.65 - 7.71 (m, 1 H).

Reference： [1]Patent: WO2012/120023,2012,A1 .Location in patent: Page/Page column 48

39
[ 1056418-83-7 ]
[ 67492-50-6 ]
[ 1056416-83-1 ]

Yield	Reaction Conditions	Operation in experiment
	With N-Methyldicyclohexylamine;bis(tri-t-butylphosphine)palladium(0); In 1,4-dioxane; at 110℃; for 0.333333h;microwave irradiation;	To a solution of 5-chloro-N-(3,4- dimethoxybenzyl)-2,3'-bipyridine-3-carboxamide (0.600 g, 1.56 mmol) in dioxane (5.2 mL) was added <strong>[67492-50-6]3,5-dichlorophenyl boronic acid</strong> (1.50 g, 7.82 mmol), N,N-dicylohexylmethylamine (0.368 mL, 1.72 mmol), and bis(tri-t-butylphosphine)palladium(0.023 g, 0.047 mmol) and the system was stirred at HO0C for 20 minutes in the microwave. The reaction was then cooled to room temperature, and partitioned between ethyl acetate and water. The reaction mixture was filtered and purified via normal phase chromatography (0-->6percent MeOH in DCM) followed by reverse phase chromatography ( 10percent-->65percent 0.1 percent TFA in water: 0.1 percent TFA in ACN) followed by free basing with saturated sodium carbonate afforded the title compound (2J.) as a white powder. 1H NMR (500 MHz, CDCl3) delta 9.00 (s, IH), 8.95 (s, IH), 8.66-8.68 (m, IH), 8.15 (s, IH), 7.98-8.00 (m, IH), 7.53-7.54 (m, 2H), 7.46-7.47 (m, IH), 7.28-7.30 (m, IH), 6.77 (d, J= 5Hz, IH), 6.39- 6.66 (m, 2H), 5.69 (br s, IH), 4.42 (d, J= 5.5Hz, 2H), 3.85 (s, 3H), 3.88 (s, 3H). HRMS [M+H] C26H2ICl2N3O3 calc'd 494.1033, found 494.1023.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 6620 - 6624
[2]Patent: WO2008/108991,2008,A1 .Location in patent: Page/Page column 31-32

40
[ 20780-75-0 ]
[ 67492-50-6 ]
[ 1421700-88-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In 1,2-dimethoxyethane; water; at 130℃; for 0.0833333h;Microwave irradiation; Inert atmosphere;	General procedure: General procedure for the synthesis of compounds 4-39; 4-Iodoisatin 1 (50.0 mg, 0.183 mmol) and 3a (22.3 mg, 0.183 mmol) were dissolved in DME (3 mL) and H2O (0.6 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (5 mmol percent, 11 mg) and sodium bicarbonate (30.7 mg, 0.366 mmol) were added, and the reaction mixture was irradiated in a microwave apparatus at 130 °C for 4-12 min. After the reaction mixture was cooled to ambient temperature, the product was concentrated, and the crude mixture was purified by silica gel column chromatography using petroleum ether/acetone (20/1 to 10/1) as eluent to give the title compound 4. 4-(3,5-Dichlorophenyl)indoline-2,3-dione (20) Orange solid, 44.3 mg, 83percent yield; mp: 310-311 °C. 1H NMR (400 MHz, dmso) delta 11.16 (s, 1H), 7.69 (s, 1H), 7.66-7.57 (m, 3H), 7.07 (d, J = 7.8 Hz, 1H), 6.94 (d, J = 7.8 Hz, 1H). 13C NMR (100 MHz, dmso) delta 182.81, 158.96, 151.34, 139.59, 137.86, 137.77, 133.68, 127.94, 127.54, 124.01, 114.42, 112.17. MS: m/z = 291.11 (M+). Anal. Calcd for (C14H7Cl2NO2): C, 57.56; H, 2.42; N, 4.79. Found: C, 57.79; H, 2.34; N, 4.91.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 949 - 955

41
[ 1427000-64-3 ]
[ 67492-50-6 ]
[ 1427000-84-7 ]

Yield	Reaction Conditions	Operation in experiment
96%	With palladium diacetate; cesium fluoride; johnphos; In tetrahydrofuran; at 50℃; for 8h;Inert atmosphere;	A 100 mL flask purged with nitrogen was loaded with 300 mg of 4 , 5 , 6, 7-tetrahydro-3- ( 2 , 6-dibromophenyl ) -2 ( 3H) - benzothiazole-thione synthesized the same as in Example 6, 430 mg of 3 , 5-dichlorophenylboronic acid, 10 g of tetrahydrofuran, 70 mg of (2-di-tert- butylphosphino) biphenyl, 700 mg of cesium fluoride, and 17 mg of palladium acetate and the mixture was heated to 50°C and stirred for 8 hours. After the reaction, the reaction solution was mixed with 10 g of ethyl acetate and 20 g of water and washed and separated by a separatory funnel. The formed organic layer was again washed and separated with 10 g of water and thereafter dried with magnesium sulfate and the solvent was removed by distillation. The obtained residue was refined by a. silica gel short column (adsorption in 50 g of silica gel and thereafter, elution with 300 mL of chloroform) and the sdistillation to obtain 380 mg of a light yellow crystal. This crystal was confirmed to be 4 , 5 , 6 , 7-tetrahydro-3- [2 , 6- bis ( 3 , 5-dichlorophenyl ) phenyl ] -2 ( 3H) -benzothiazole-thione by GC-MS. Yield 96percent, M+ = 537.

Reference： [1]Patent: WO2013/35650,2013,A1 .Location in patent: Paragraph 0162

42
C₁₈H₂₄BrNO₄ [ No CAS ]
[ 67492-50-6 ]
C₂₄H₂₇Cl₂NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In N,N-dimethyl-formamide; at 95℃; for 6h;Inert atmosphere;	General procedure: To the solution of I-5 (21.54 g, 57 mmol) and 3,5-dichlorophenylboronic acid (13.00 g, 68 mmol) in 260 mL of N,N-dimethylformamide was added Pd(dppf)Cl2 (0.64 g) and 2 M Na2CO3(75.00 g) under nitrogen. The resulting mixture was stirred at 95° C. for 6 hrs, cooled to room temperature, poured into 600 mL of water, extracted with ethyl acetate (2×400 mL) and washed with saturated brine. Removal of the solvent in vacuo afforded a residue that was purified by flash column chromatography to afford I-6 (15.00 g, 56percent) as a white solid. 1H-NMR (400 MHz, DMSO-d6): delta 7.71-7.67 (m, 4H), 7.57 (s, 1H), 7.36 (d, J=8.0 Hz, 2H), 7.23 (d, J=8.4 Hz, 1H), 6.92 (dd, J=15.6, 5.2 Hz, 1H), 5.88 (d, J=15.6 Hz, 1H), 4.40 (brs, 1H), 4.15 (q, J=6.8 Hz, 2H), 2.94-2.90 (m, 1H), 2.77-2.72 (m, 1H), 1.31 (s, 9H), 1.23 (t, J=6.8 Hz, 3H).

Reference： [1]Patent: US2013/102649,2013,A1 .Location in patent: Paragraph 0264

43
[ 68318-95-6 ]
[ 67492-50-6 ]
[ 864736-73-2 ]

Yield	Reaction Conditions	Operation in experiment
66%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; water; at 80℃; for 4h;Sealed tube;	Step 1: Preparation of 1,3-dichloro-5-(3,3,4,4,4-pentafluorobut-1-en-2-yl)benzene A mixture of 3,5-dichlorophenylboronic acid (793 mg, 4.15 mmol), 2-bromo-3,3,4,4,4-pentafluorobut-1-ene (1.0 g, 4.57 mmol), K2CO3 (1.14 g, 8.3 mmol) and Pd(PPh3)2Cl2 (58 mg, 0.08 mmol) in THF (4 mL) and H2O (2 mL) was heated at 80° C. in a sealed tube for 4 h. The mixture was cooled to rt and partitioned between EA (50 mL) and H2O (50 mL). The aqueous layer was extracted with EA (50 mL) and the combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure and the crude product was purified by column chromatography on silica gel to give the crude desired product (800 mg; 66percent yield) as colorless oil.

Reference： [1]Patent: US2013/131016,2013,A1 .Location in patent: Paragraph 0245

44
[ 29681-42-3 ]
[ 67492-50-6 ]
C₁₂H₆Cl₂NO₂^(1-)*K⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; at 90℃; for 16h;Inert atmosphere;	[00241] Referring to Reaction Scheme 25, Stage 1, to a stirred suspension of 4- bromo-pyridine-2-carboxylic acid methyl ester (leq) in 1,4-dioxane (20vol) was added the appropriate substituted phenyl boronic acid (l . leq) and Pd(PPh3)4 (0.05eq). A 2M K2C03 solution (7.5vol) was added and the reaction mixture was heated at 90C with stirring for 16 hours under an atmosphere of N2. The reaction mixture was cooled to room temperature and the resulting precipitate was isolated by filtration to furnish the acid intermediate as the potassium salt, which was used without further purification in the stage. In the case of the 3-chlorophenyl analogue no precipitate was formed upon cooling, hence the solvent was removed in vacuo. The resulting residue was dissolved in EtOAc and water. Both phases were separated. EtOAc was removed in vacuo and the resulting residue was purified by flash column chromatography (eluent: [5:95] methanol:DCM) to furnish the desired 4-(3-chloro-phenyl)-pyridine-2-carboxylic acid methyl ester.

Reference： [1]Patent: WO2013/33068,2013,A1 .Location in patent: Paragraph 00241

45
[ 1236563-13-5 ]
[ 67492-50-6 ]
[ 1456799-00-0 ]

Yield	Reaction Conditions	Operation in experiment
97%	With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In 1,2-dimethoxyethane; water; at 110℃; for 0.0833333h;Inert atmosphere; Microwave irradiation;	General procedure: Aryl iodide 1 (152 mg, 0.5 mmol) and 2a (61 mg, 0.5 mmol) were dissolved in DME (3 mL) and H2O (0.6 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (0.005 mmol, 5.78 mg) and sodium bicarbonate (84 mg, 1 mmol) were added, and the reaction mixture was irradiated in a microwave apparatus at 110 oC for 4-10 min. After the reaction mixture was cooled to ambient temperature, the product was concentrated, and the crude mixture was purified by silica gel column chromatography using petroleum ether/acetone (20/1 to 10/1) as eluent to give the title compound 3a (122 mg) in 96percent yield.

Reference： [1]Tetrahedron,2013,vol. 69,p. 9025 - 9032

46
[ 104-92-7 ]
[ 67492-50-6 ]
[ 1033945-05-9 ]

Yield	Reaction Conditions	Operation in experiment
94%	With dichloro bis(acetonitrile) palladium(II); C10H11N3S; potassium carbonate; In water; N,N-dimethyl-formamide; at 20℃; for 1h;Schlenk technique; Inert atmosphere;	General procedure: An oven-dried Schlenk tube was charged with 2a (1.2 mmol), Pd(CH3CN)2Cl2 (0.1 mol%), L1(0.1 mol%), anhydrous K2CO3 (2 mmol).The Schlenk tube was backfilled with argon for three times. Then,DMF/H2O (2:1) (3 mL) was added by syringe, followed by additionof 1a (1 mmol) in a similar manner (solids were added with otherreagents before evacuation). The reaction was stirred in room temperatureand was monitored by TLC. After 1 h, the reaction mixturewas added water (50 mL), and then extracted with ethyl acetate(50 mL x 3). The combined organic layer was washed with brineand was dried over anhydrous Na2SO4. After filtered and concentratedunder reduced pressure, the residue was purified by columnchromatography on silica gel (Petroleum ether as eluent) to yieldthe product.

Reference： [1]Journal of Catalysis,2019,vol. 376,p. 101 - 105
[2]Journal of Medicinal Chemistry,2013,vol. 56,p. 7334 - 7342

47
[ 1469858-10-3 ]
[ 67492-50-6 ]
[ 1469858-27-2 ]

Yield	Reaction Conditions	Operation in experiment
53%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; toluene; at 100℃; for 8h;	A mixture of the corresponding intermediate 6-(4-Bromo-phenyl)-4-(2-trimethylsilanyl-ethoxymethyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pental ene (1.46 g, 32 mmol), 3,5-Dichlorophenylboronic acid (0.94 g, 49 mmol), Na2CO3 (2 M, 7 mL), and Pd(PPh3)2Cl2 (30 mg, 0.26 mmol) in toluene/ ethanol (1:1, 18 mL) was heated at 100° C. for 8 hr. The solution was cooled to room temperature and extracted with ethyl acetate. The target product was purified by gravity column chromatography (20percent EtOAc in hexane) to give 6-(3?,5?-Dichloro-biphenyl-4-yl) {4-[4-(2-trimethylsilanyl-ethoxymethyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalene as brown solid in 53percent yield.
53%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; toluene; at 100℃; for 8h;	The corresponding intermediate 6- (4-bromo-phenyl) -4- (2-trimethylsilane-ethoxymethyl) -4,7-dihydro-1, Cyclopentadiene (1.46 g, 32 mmol), 3,5-dichlorophenylboronic acid (0.94 g, 49 mmol), Na2CO3 (2 M, 7 mL) and Pd ( PPh3) 2Cl2 (30 mg, 0.26 mmol) in toluene / ethanol (1: 1, 18 mL) was heated to 100 & lt; 0 & gt; C and maintained for 8 hours. The solution was cooled to room temperature and extracted with ethyl acetate. The target product was obtained as a brown solid by gravity column chromatography (20percent EtOAc in hexanes)6- (3 ', 5'-dichloro-biphenyl-4-yl) {4- [4- (2-trimethylsilane-ethoxymethyl) -4,7-dihydro- -4,5-diazo-cyclopenta [a] cyclopentadiene, 53percent yield.

Reference： [1]Patent: US2013/274255,2013,A1 .Location in patent: Paragraph 0221
[2]Patent: TWI553010,2016,B .Location in patent: Page/Page column 53

48
[ 78686-83-6 ]
[ 67492-50-6 ]
methyl 2-chloro-5-(3,5-dichlorophenyl)nicotinate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; water; caesium carbonate; In N,N-dimethyl-formamide; at 0 - 25℃; for 3h;	To a solution of methyl-2-chloro-5-iodonicotinate (19, 5.0 g, 16.8 mmol) and 3,5-dichlorophenyl boronic ester (3.21g, 16.8 mmol) in DMF (84 mL, 0.2 M) at 0oC was added cesium carbonate (19.2 g, 58.8 mmol), PdCl2(dppf) (1.23 g, 1.68 mmol) and water (3.0 mL, 168 mmol). The system was then stirred for 3h as it approached ambient temperature. The crude reaction mixture was partitioned with water and EtOAc, washed with brine and dried over magnesium sulfate. Filtration, concentration, and purification on silica (0 ? 15% EtOAc/Hexanes) afforded 20 as a white powder (3.0 g, 56 % yield). ESI+ MS C13H8Cl3NO2: 315.9 found, 315.9 required.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 6620 - 6624

49
[ 1466608-46-7 ]
[ 67492-50-6 ]
9-(3",5"-dichloro-[1,1':2',1"-terphenyl]-3-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 24h;Inert atmosphere; Reflux;	9-(2?-Bromo-[1,1?-biphenyl]-3-yl)-9H-carbazole (10.0g, 25.1mmol), 3,5-dichlorophenylboronic acid (6.23g, 32.6mmol) and tetrahydrofuran (240ml) were added to a two-necked flask and was bubbled with nitrogen for 30min. Potassium carbonate (8.68g, 62.8mmol) dissolved in oxygen free distilled water (80ml) was added to the solution followed by adding Pd(PPh3)4 (1.45g, 1.26mmol). The resulting suspension was refluxed for 24h under nitrogen. The reaction was allowed to cool and was extracted with ethyl acetate. The organic layer was combined, washed with water saturated with sodium chloride, and dried over magnesium sulfate. Solvent was removed with a rotary evaporator to yield a brown powder, which was purified by column chromatography using a dichloromethane/n-hexane eluent to give 9-(3?,5?-dichloro-[1,1?:2?,1?-terphenyl]-3-yl)-9H-carbazole (9.0g) as a white powder.

Reference： [1]Dyes and Pigments,2014,vol. 101,p. 150 - 155

50
[ 591-50-4 ]
[ 67492-50-6 ]
[ 34883-41-5 ]

Yield	Reaction Conditions	Operation in experiment
87%	With dichlorido(2,2'-(4-phenoxy-1,2-phenylene)bis(4,4-dimethyl-4,5-dihydrooxazole)-N,N')palladium(II); potassium carbonate; In N,N-dimethyl-formamide; at 70℃; for 6h;Inert atmosphere;	General procedure: The reaction was conducted in a 15 mL round bottom flask. Aryl halide (0.50 mmol), phenylboronic acid (0.60 mmol), Pd?BOX complex (0.010 mmol), K2CO3 (2.0 mmol), DMF (5.0 mL) was stirred for 6 h at 70 °C under argon. After completion of the reaction, the mixture was cooled down to room temperature, filtered and immediately analyzed by GC and GC?MS. The GC yield was determined based on the amount of aryl halide. The reaction mixture was washed with H2O and EtOAc and the organic layer was dried using MgSO4. The solvent was removed under reduced pressure and the product was separated by column chromatography using hexane?EtOAc (90:10) solvent system to give the pure products. The characterization data of the compounds 5a [27], 5d [27], 5f [27], 5g [27], 5b [28], 5c [29] and 5e [30] were in total agreement with those observed in literature.#10;#10;

Reference： [1]Polyhedron,2014,vol. 70,p. 39 - 46

51
[ 1236568-49-2 ]
[ 67492-50-6 ]
[ 1590352-44-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydrogencarbonate; In water; toluene; at 120℃; for 0.1h;Inert atmosphere; Microwave irradiation;	General procedure: Aryl iodide 1 (160 mg, 0.5 mmol) and 2a (61 mg, 0.5 mmol) were dissolved in toluene (3 mL) and H2O (0.6 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (0.01 mmol, 11.56 mg), sodium bicarbonate (84 mg, 1 mmol), and tetrabutyl ammonium bromide (80.5 mg, 0.25 mmol) were added, and then the reaction mixture was irradiated in a microwave apparatus at 120 °C for 6?13 min. After the reaction mixture was cooled to ambient temperature, the reaction mixture was concentrated, and the crude residue was purified by silica gel column chromatography using petroleum ether/acetone (20/1 to 10/1) as eluent to give the title compound 3a (123 mg) in 91percent yield.

Reference： [1]Tetrahedron,2014,vol. 70,p. 2746 - 2752

52
[ 67492-50-6 ]
[ 931-59-9 ]
(3,5-dichlorophenyl)(phenyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With Pd(2-[2-(benzylthio)phenyliminomethyl]-4-bromophenol-(H))Cl; potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 5h;Sealed tube; Inert atmosphere;	General procedure: A sealed tube was charged with sulfenyl chloride 2a (219mg, 1 mmol), phenylboronic acid (3a) (135 mg, 1 mmol),K2CO3 (254 mg, 2 mmol), catalyst 1a (2 molpercent, 10 mg) andDMF (2 mL). The mixture was stirred at 90 °C under an N2atm for 5 h. After completion of the reaction, the mixturewas cooled to r.t. and extracted with EtOAc (2 × 10 mL). The combined extracts were dried over anhydrous Na2SO4,filtered and the solvent removed under reduced pressure.The crude residue was purified by flash chromatographyover silica gel to provide product 4a (166 mg, 89percent).

Reference： [1]Synlett,2014,vol. 25,p. 866 - 870

53
[ 39806-90-1 ]
[ 67492-50-6 ]
[ 1610802-73-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; water; at 90℃; for 0.0833333h;Microwave irradiation; Inert atmosphere;	General procedure: 4-Iodo-1-methyl-1H-pyrazole 1 (101 mg, 0.5 mmol) and phenylboronic 2 (59 mg, 0.5 mmol) were dissolved in DME (3 mL) and H2O (1.2 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (2 mmolpercent, 11.6 mg) and Cs2CO3 (407.3 mg, 1.25 mmol) were added, and the reaction mixture was irradiated in a microwave apparatus at 90 °C for 5?12 min. After the reaction mixture was cooled to ambient temperature, the product was concentrated, and the crude mixture was purified by silica gel column chromatography using petroleum ether/acetone as eluent to give the title compound.

Reference： [1]Chinese Chemical Letters,2014,vol. 25,p. 705 - 709

54
[ 61830-23-7 ]
[ 67492-50-6 ]
[ 127918-27-8 ]

Yield	Reaction Conditions	Operation in experiment
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 90℃; for 5h;	General procedure: 4.1.1 Methyl 3-phenylthiophene-2-carboxylate (5) Tetrakis(triphenylphosphine)palladium (5.49 g, 4.75 mmol) and 2 M aqueous disodium carbonate (71 mL) were added to a mixture of methyl 3-bromothiophene-2-carboxylate (1, 21 g, 95.0 mmol), phenylboronic acid (13.9 g, 114 mmol) and 1,4-dioxane (210 mL), and the mixture was stirred for 5 h at 90 C. The reaction mixture was cooled to room temperature and then diluted with H2O and extracted with AcOEt. The organic layer was washed successively with H2O and saturated aqueous NaCl and then dried and concentrated in vacuo. The residue was chromatographed on silica gel with elution using hexane/AcOEt (9:1 to 4:1) to produce the desired compound 5 (14.4 g, 70%) as a colorless solid which was used in the next reaction without recrystallization. 4.1.8 Ethyl 5-(3,5-dichlorophenyl)-1,3-thiazole-4-carboxylate (12) Compound 12 was prepared from 4 and (3,5-dichlorophenyl)boronic acid in 63% yield as a yellow solid, using an approach similar to that described for 5, and was used in the next reaction without further purification. 1H NMR (DMSO-d6) delta 1.14 (3H, t, J = 7.2 Hz), 4.18 (2H, q, J = 7.2 Hz), 7.65 (2H, d, J = 2.0 Hz), 7.74 (1H, t, J = 2.0 Hz), 9.20(1H, s); FAB MS m/e [M+H]+ 302.

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 3478 - 3487

55
[ 373-88-6 ]
[ 67492-50-6 ]
[ 1360594-85-9 ]

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 4477 - 4481

56
[ 108-86-1 ]
[ 67492-50-6 ]
[ 34883-41-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	With Pd/C; potassium carbonate; In water; N,N-dimethyl-formamide; at 40℃; for 2.5h;	General procedure: To a tube equipped with a magnetic stir bar were added catalyst 1(7.0 mg, 0.1 molpercent Pd), K2CO3 (138 mg, 2.0 equiv), arylboronicacid (1.1 equiv), and aryl bromide (0.5 mmol) in turn. Subsequently,the solvent (DMF?H2O, 3:2, 2.0 mL, v/v) was added under an airatmosphere. The reaction was then heated to 40 °C and stirred untilthe aryl bromide was completely consumed as determined by TLC.After completion of the reaction, the reaction mixture was purifiedby silica gel column chromatography to afford the desired pureproduct.

Reference： [1]Synthesis,2014,vol. 46,p. 1593 - 1602

57
[ 67492-50-6 ]
[ 591-35-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper(ll) sulfate pentahydrate; ellagic acid; In methanol; at 60℃; under 760.051 Torr; for 8h;Green chemistry;	General procedure: In a typical reaction, 10 mol% CuSO4·5H2O, (0.049 g, 0.2 mmol)and 6.7 mol% EA (20 mg) were mixed in methanol followed by2 mmol of phenylboronic acid. This reaction mixture was kept ina preheated oil bath by maintaining the temperature at 60 C andstirred under atmospheric pressure. After completion of the reac-tion, modified by TLC, the mixture was washed twice with hot ethylacetate to remove the reactant and product. The hot ethyl acetatewas removed from the reaction mixture and the resulting crudeproduct was purified by a column chromatography using silicagel 260 mesh (pet ether:ethyl acetate) ratio (25:75). The recov-ered catalyst was reused for the next run. All the products werecharacterized by1H and13C NMR spectra.

Reference： [1]Journal of Molecular Catalysis A: Chemical,2014,vol. 395,p. 500 - 505

58
[ 32601-86-8 ]
[ 67492-50-6 ]
2-(3,5-dichlorophenyl)-3-methylquinoxaline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 19h;Inert atmosphere;	[0201] H3C CH3 H3C CH3 boronic acid, 1.68 g of potassium carbonate, 0.049 g of tri(otolyl)phosphine, 20 mL of toluene, 5 mL of ethanol, and 6 mL of water were put in a three-neck flask equipped with a reflux pipe, and the air in the flask was replaced with nitrogen. The inside of the flask was degassed under reduced pressure, 0.018 g of palladium acetate was added thereto, and the mixture was heated at 80 C for 19 hours. Then, water was added to this solution, and the organic layer was extracted with toluene. The obtained organic layer was washed with water and saturated saline, and was dried with magnesium sulfate. The solution obtained by the drying was filtered. The solvent of this solution was distilled off, and then the obtained residue was purified by flash column chromatography using hexane and ethyl acetate in a volume ratio of 5: 1 as a developing solvent to give a target quinoxaline derivative as pale pink powder in a yield of 67 %). Synthesis Scheme (c-1) of Step 1 is shown below.

Reference： [1]Patent: WO2014/199842,2014,A1 .Location in patent: Paragraph 0202-0203

59
[ 616-45-5 ]
[ 67492-50-6 ]
1-(3,5-dichlorophenyl)pyrrolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%		General procedure: Aryl boronic acid (1.0 mmol), CuI (5 molpercent),amide (3.0 mmol), and DMSO (1.0 mL) were added to a reactionvial, and the mixture was stirred at room temperature for10 min. A 70percent aqueous solution of TBHP (1.1 mmol) was addedto the reaction mixture dropwise over 5 min. The reaction vialwas then immersed in a preheated oil bath and the progress ofreaction was followed by TLC. Upon completion of reaction, thecooled mixture was partitioned between water and ethyl acetate.The aqueous layer was further extracted with ethyl acetate,and the combined organic layers were washed with brine,dried over Na2SO4, filtered, and concentrated in vacuo. Theresidue was purified by column chromatography on silica gel(hexane?ethyl acetate) to give the desired N-aryl lactam

Reference： [1]Synlett,2015,vol. 26,p. 1348 - 1351

60
[ 67492-50-6 ]
[ 134-96-3 ]
[ 1055351-98-8 ]

Yield	Reaction Conditions	Operation in experiment
82%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; N,N-dimethyl-formamide; at 40℃; for 16h;Inert atmosphere; Sealed tube;	Reactions were conducted in an 8 well aluminum block in 25 * 150 test tubes and 8 reaction were pooled for workup. To degassed dimethylformamide (14 mL) was added tetrakis(triphenylphosphine)palladium(0) (184 mg, 0.16 mmol) and the mixture was heated to 40 °C for 30 min to dissolve the catalyst then cooled to room temperature. To the solution was added 2 (1 g, 3.18 mmol) with stirring to dissolve then 3,5-dichlorophenylboronic acid (1.21 g, 6.36 mmol), degassed water (3 mL), and sodium carbonate (675 mg, 6.36 mmol) were added sequentially. Tubes were blanked with nitrogen, sealed with a septum, and heated to 40 °C for 16 h. Reactions were pooled and filtered through a 0.5 * 4.5 cm Celite pad and the pad washed with 40 mL ethyl acetate. To the filtrate was added 100 mL water and the mixture was extracted with ethyl acetate (3 * 40 mL). The organic phase was extracted with water (3 * 30 mL) and brine (30 mL) and dried with sodium sulfate.The residue after solvent removal was dissolved in dichloromethane(10 mL) and loaded on a Grace Reveleris 120 g silica columnand eluted with a hexane/ethyl acetate gradient (5?5percent 2column volumes, 5?40percent 10 column volumes, 40?40percent 2 columnvolume, flow rate 80 mL per min). Product fractions were pooledand dried yielding 6.52 g (82percent) of 3 as white crystals. 1H NMR,(400 MHz, CDCl3), d 9.98 (s, 1H, CHO), 7.34 (t, J = 2.0 Hz, 1H,40ArH), 7.21 (d, J = 2.0 Hz, 2H, 20,60ArH), 7.15 (s, 2H, 2,6ArH), 3.83(s, 6H, OCH3), MS: m/z (ESI, pos.) = 333.6 [M+23]+.

Reference： [1]Bioorganic and Medicinal Chemistry,2015,vol. 23,p. 5390 - 5401

61
[ 67492-50-6 ]
[ 164014-40-8 ]
[ 1456799-00-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In 1,2-dimethoxyethane; water; at 110℃; for 0.1h;Inert atmosphere; Microwave irradiation;	General procedure: Aryl salicylates 1 or 8 (0.5 mmol) and 2a (0.5 mmol) were dissolved in DME (3 mL) and H2O (0.6 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (0.005 mmol) and sodium bicarbonate (1 mmol) were added, and the reaction mixture was irradiatedin a microwave apparatus at 110 C for 4-10 min. After the reaction mixture was cooled to ambient temperature, the product was concentrated, and the crude mixture was purified by silica gel column chromatography using petroleum ether/acetone (20/1 to10/1) as eluent to give the title compound 3a in 94percent yield and 9a in 92percent yield.

Reference： [1]Tetrahedron,2015,vol. 71,p. 8123 - 8130

62
[ 93131-78-3 ]
[ 67492-50-6 ]
7-(3,5-dichlorophenyl)-4-methyl-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With 1,3-bis-(diphenylphosphino)propane; palladium diacetate; tetra-n-butylammoniumfluoride trihydrate; In methanol; 1,2-dimethoxyethane; at 20 - 80℃; for 0.5h;Inert atmosphere; Microwave irradiation;	General procedure: To a solution of 4-methyl-7-nonauorobutylsulfonyloxy coumarin (3b, 1 equiv.) in DME?MeOH (3:1), were added Pd(OAc) 2(0.05 equiv.) and dppp (0.1 equiv.). The solution was purged with nitrogen and stirred at room temperature for 10 min, at which time boronic acid (1.5 equiv.) and TBAF 3H2O (3 equiv.) was added. The reaction solution was purged again with nitrogen and then placed in the microwave and heated for 20?30 min at 80°C at 110 W. When TLC and LC?MS showed full consumption of starting materials, the reaction mixture was diluted with ethyl acetate, separated the organic layer, given water wash, brine wash and was dried over anhydrous sodium sulfate and distilled under reduced pressure to get the crude material. The crude product was further puried by column chromatography and eluted in varying polarities to obtain the diaryls 4a?x.

Reference： [1]Journal of Fluorine Chemistry,2016,vol. 182,p. 109 - 120

63
[ 122306-01-8 ]
[ 67492-50-6 ]
[6-(3,5-dichlorophenyl)pyridin-3-yl]methanol [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2015,vol. 54,p. 14287 - 14290
Angew. Chem.,2015,vol. 147,p. 14495 - 14498,4

64
[ 28342-75-8 ]
[ 67492-50-6 ]
1,5-bis(3,5-dichlorophenyl)-2,4-difluorobenzene [ No CAS ]

Reference： [1]Journal of Materials Chemistry C,2016,vol. 4,p. 1104 - 1110

65
[ 6011-14-9 ]
[ 67492-50-6 ]
[ 52516-37-7 ]

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 10510 - 10514
Angew. Chem.,2014,vol. 126,p. 10678 - 10682,5

66
[ 67492-50-6 ]
[ 415718-60-4 ]
2-(4-cyanophenyl)-5-(3,5-dichlorophenyl)thiophene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate; In methanol; water; toluene; at 80℃; for 16h;	General procedure: To a stirred solution of the appropriate bromobenzonitrile (5 mmol), and tetrakis(triphenyl-phosphine) palladium (150 mg) intoluene (10 mL) was added 5 mL of a 1.5 M aqueous solution ofNaHCO3 followed by phenylboronic acid derivative (6 mmol) in5 mL of methanol. The vigorously stirred reaction mixture waswarmed to 80 °C for 16 h. The solvent was then evaporated todryness, and the solid residue was partitioned between methylenechloride (250 mL) and an aqueous solution containing 5 mLconcentrated ammonia. The target diarylthiophene carbonitrileswere obtained from the methylene chloride layer upon evaporationto dryness under vacuum

Reference： [1]European Journal of Medicinal Chemistry,2017,vol. 126,p. 789 - 798

67
[ 23449-08-3 ]
[ 67492-50-6 ]
C₂₇H₁₇Cl₂N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 90℃; for 1h;	4-bromo-triazine (20g, 51.5mmol) and 3,5-phenylboronic acid(9.8g, 51.5mmol) and potassium carbonate (K2CO3) (21.3g, 155mmol) intetrahydrofuran (THF) (300mL) , dissolved in H2O (100ml) and it was heated to 90°C. And tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4) (1.2 g,1.03 mmol) was added and refluxed for 1 hour. After cooling to room temperature, the water layer was removed. Magnesium sulfate (MgSO4) was added to the organic layer and then filtered. And after Concentrated ,purified by column chromatography to obtain the compound of formula 1A (21 g, yield 90percent).

Reference： [1]Patent: KR2015/140241,2015,A .Location in patent: Paragraph 0246-0248; 0252-0255

68
[ 67492-50-6 ]
3-(4-bromophenyl)-2-hydroxypropionic acid methyl ester [ No CAS ]
C₁₆H₁₄Cl₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; at 150℃; for 3h;Inert atmosphere;	3- (4-bromophenyl) -2-hydroxypropionic acid methyl ester (500 mg, 1.93 mmol), 3,5- dichlorophenyl boronic acid (442 mg, 2.32 mmol), [1,1'- bis (diphenylphosphino) ferrocene] dichloropalladium (II), dichloromethane adduct (79 mg), potassium carbonate (400 mg, 2.90 mmol) and dioxane (10 ml), under a nitrogen atmosphere and stirred for 3 hours at 150° C.. The reaction was concentrated under reduced pressure, directly by silica gel chromatography (hexane: 1: ethyl acetate = 4). This gave the title compound (yellow oil 441 mg, 70percent).

Reference： [1]Patent: JP6037277,2016,B2 .Location in patent: Paragraph 0079; 0080

69
methyl 4-bromo-1-(4-(3,4-dichlorophenyl)-5-(isopropylthio)thiazol-2-yl)-3-methyl-1H-pyrazole-5-carboxylate [ No CAS ]
[ 67492-50-6 ]
4-(3,5-dichlorophenyl)-1-(4-(3,4-dichlorophenyl)-5-(isopropylthio)thiazol-2-yl)-3-methyl-1H-pyrazole-5-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
27%		Nitrogen was passed through a solution of dioxane/H2O (4/1) and this solution (2.0 mL) was then added to a mixture of the methyl 4-bromo-1-(4-(3,4-dichlorophenyl)-5- (isopropylthio)thiazol-2-yl)-3-methyl-1H-pyrazole-5-carboxylate (50 mg, 0.096 mmol), (3,5- dichlorophenyl)boronic acid ( 23 mg, 0.12 mmol) and Na2CO3 (51 mg, 0.48 mmol) followed by the addition of the catalyst Pd(PPh3)4 (11 mg, 0.010 mmol). The reaction mixture was heated at 85 oC for 16 hours. Add LiOH (12 mg, 0.48 mmol) and the reaction mixture was stirred in the microwave at 110 oC for 10 min. More LiOH (12 mg, 0.48 mmol) was added and stirring in the microwave at 110 oC was continued for 30 min. Evaporated in vacuo. The crude product was purified by semi-prep HPLC-MS (column X-Bridge 30x50, eluted with 65- 85percent MeCN/NH4CO2H 10 mM, pH 3.8/Flow 45 ml/min/10 min) and afforded the title compound (15 mg, 0.026 mmol, 27percent) as a yellow solid after lyophilization. 1H NMR (500 MHz, DMSO) delta 8.19 (d, J = 2.1 Hz, 1H), 8.01 (dd, J = 8.5, 2.1 Hz, 1H), 777 (d, J = 8.5 Hz, 1H), 7.68-7.65(m, 1H), 7.54 (d, J = 1.9 Hz, 2H), 3.42? 3.32 (m, 1H), 2.31 (s, 3H), 1.24 (d, J = 6.7 Hz, 6H). MS (m/z): 571.8 [M+1]+.
27%		Nitrogen was passed through a solution of dioxane/H20 (4/1) and this solution (2.0 mL) was then added to a mixture of the methyl 4-bromo-1-(4-(3,4-dichlorophenyl)-5- (isopropylthio)thiazol-2-yl)-3-methyl- 1 H-pyrazole-5-carboxylate (50 mg, 0.096 mmol), (3,5- dichlorophenyl)boronic acid (23 mg, 0.12 mmol) and Na2003 (51 mg, 0.48 mmol) followed by the addition of the catalyst Pd(PPh3)4 (11 mg, 0.010 mmol). The reaction mixture was heated at 85 00 for 16 hours. Add LiOH (12 mg, 0.48 mmol) and the reaction mixture was stirred in the microwave at 11000 for 10 mm. More LiOH (12 mg, 0.48 mmol) was added and stirring in the microwave at 110 00 was continued for 30 mm. Evaporated in vacuo. The crude product was purified by semi-prep H PLC-MS (column X-Bridge 30x50, eluted with 65- 85percent MeCN/NH4002H 10 mM, pH 3.8/Flow 45 mI/min/lO mm) and afforded the title compound (15 mg, 0.026 mmol, 27percent) as a yellow solid after lyophilization. 1H NMR (500 MHz, DMSO) O 8.19 (d, J= 2.1 Hz, 1H), 8.01 (dd, J= 8.5, 2.1 Hz, 1 H), 777 (d, J = 8.5 Hz, 1 H), 7.68-7.65(m, 1 H), 7.54 (d, J = 1.9 Hz, 2H), 3.42 ? 3.32 (m, 1 H),2.31 (5, 3H), 1.24 (d, J= 6.7 Hz, 6H). MS (m/z): 571.8 [M+1]+.

Reference： [1]Patent: WO2016/196644,2016,A1 .Location in patent: Paragraph 475; 476
[2]Patent: WO2018/102452,2018,A2 .Location in patent: Paragraph 459; 460
[3]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 4471 - 4477

70
methyl 4-bromo-1-(5-(sec-butylthio)-4-(3,4-dichlorophenyl)thiazol-2-yl)-3-methyl-1H-pyrazole-5-carboxylate [ No CAS ]
[ 67492-50-6 ]
methyl 1-(5-(sec-butylthio)-4-(3,4-dichlorophenyl)thiazol-2-yl)-4-(3,5-dichlorophenyl)-3-methyl-1H-pyrazole-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 85℃; for 16h;Inert atmosphere; Sealed tube;	In a 5 mL glass microwave vial equipped with a magnetic stirring bar and nitrogen flow at room temperature was placed methyl 4-bromo-1-(5-(sec-butylthio)-4-(3,4- dichlorophenyl)thiazol-2-yl)-3-methyl-1H-pyrazole-5-carboxylate (150.0 mg, 0.280 mmol), 3,5-dichlorophenylboronic acid (49.4 mg, 0.26 mmol) and Na2CO3 (114 mg, 1.08 mmol), nitrogen and vacuum cycles were performed (2x). Nitrogen gas was bubbled through a solution of dioxane/water (2 mL, 4:1) and then the solution was added to the microwave vial, followed by the addition of the catalyst Pd(PPh3)4 (24.9 mg, 0.02 mmol). The vial was capped and placed in an oil bath at 85 °C for 16 h. The crude product was concentrated under vacuum and was purified by flash chromatography (wet loading with DCM) on silica gel using a solution of EtOAc in hexanes (2percent) and afforded the title compound (121 mg, 0.207 mmol, 74percent) as off white solid after lyophilization. 1H NMR (500 MHz, DMSO) delta 8.16 (d, J = 2.1 Hz, 1H), 7.98 (dd, J = 8.5, 2.1 Hz, 1H), 7.82 (d, J = 8.5 Hz, 1H), 7.72 (t, J = 1.9 Hz, 1H), 7.51 (d, J = 1.9 Hz, 1H), 3.82 (s, 3H), 3.22? 3.14 (m, 1H), 2.34 (s, 3H), 1.63? 1.45 (m, 2H), 1.22 (d, J = 6.8 Hz, 3H), 0.91 (t, J = 7.3 Hz, 3H); MS (m/z): 602.0 [M+1]+.
74%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 20 - 85℃; for 16h;Inert atmosphere; Sealed tube;	In a 5 mL glass microwave vial equipped with a magnetic stirring bar and nitrogenflow at room temperature was placed methyl 4-bromo-i-(5-(sec-butylthio)-4-(3,4-dichlorophenyl)thiazol-2-yl)-3-methyl-1 H-pyrazole-5-carboxylate (150.0 mg, 0.280 mmol), 3,5-dichiorophenylboronic acid (49.4 mg, 0.26 mmol) and Na2003 (114 mg, 1.08 mmol), nitrogen and vacuum cycles were performed (2x). Nitrogen gas was bubbled through a solution of dioxane/water (2 mL, 4:1) and then the solution was added to the microwave vial, followed by the addition of the catalyst Pd(PPh3)4 (24.9 mg, 0.02 mmol). The vial was capped and placed in an oil bath at 85 00 for 16 h. The crude product was concentrated under vacuum and was purified by flash chromatography (wet loading with DCM) on silica gel using a solution of EtOAc in hexanes (2percent) and afforded the title compound (121 mg, 0.207 mmol, 74percent) as off white solid after lyophilization.[254] 1H NMR (500 MHz, DMSO) O 8.16 (d, J= 2.1 Hz, 1H), 7.98 (dd, J= 8.5, 2.1 Hz, 1H), 7.82 (d, J= 8.5 Hz, 1H), 7.72 (t, J= 1.9 Hz, 1H), 7.51 (d, J= 1.9 Hz, 1H), 3.82 (5, 3H), 3.22?3.14(m, 1H), 2.34(s, 3H), 1.63? 1.45(m, 2H), 1.22 (d, J= 6.8 Hz, 3H), 0.91 (t, J=7.3 Hz, 3H); MS (m/z): 602.0 [M+1].

Reference： [1]Patent: WO2016/196644,2016,A1 .Location in patent: Paragraph 268; 269; 270
[2]Patent: WO2018/102452,2018,A2 .Location in patent: Paragraph 252; 253; 254

71
[ 10016-52-1 ]
[ 67492-50-6 ]
C₂₄H₁₂Cl₄O [ No CAS ]

Reference： [1]Patent: JP6074766,2017,B2 .Location in patent: Paragraph 0036-0037

72
[ 98-88-4 ]
[ 67492-50-6 ]
[ 13395-64-7 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium hydroxide; In toluene; at 100℃; for 2h;Schlenk technique;	General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 3201 - 3204

73
[ 122-04-3 ]
[ 67492-50-6 ]
(3,5-dichlorophenyl)(4-nitrophenyl)methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium hydroxide; In toluene; at 100℃; for 2h;Schlenk technique;	General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 3201 - 3204

74
[ 874-60-2 ]
[ 67492-50-6 ]
[ 13395-63-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium hydroxide; In toluene; at 100℃; for 2h;Schlenk technique;	General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2).

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 3201 - 3204

75
[ 677-25-8 ]
[ 67492-50-6 ]
C₈H₅Cl₂FO₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With palladium diacetate; silver nitrate; In acetic acid; at 80℃; for 12h;	250mL reaction flask,3,5-Dichlorobenzeneboronic acid (3.82 g, 20 mmol),Vinylsulfonyl fluoride (13.20 g, 120 mmol),Pd (OAc) 2 (0.22 g, 1.0 mmol, 5 molpercent),AgNO3 (5.10 g, 40 mmol),AcOH (100 mL),Heated with stirring heated to 80 reaction 12h,The reaction solution is distilled under reduced pressure to recover glacial acetic acid and vinylsulfonyl fluoride,The residue was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10: 1 (v / v)),2-phenyl-vinylsulfonyl fluoride (4.59 g, 90percent yield) was obtained.The reaction solution can also be filtered through silica gel,The filtrate was concentrated to dryness by adding diethyl ether to give the product.

Reference： [1]Patent: CN107188834,2017,A .Location in patent: Paragraph 0044; 0045; 0046

76
[ 35975-57-6 ]
[ 67492-50-6 ]
8-(3,5-dichlorophenyl)-4-hydroxyquinoline-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Under argon atmosphere a flask was charged with ethyl 8-bromo-4-hydroxy-quinoline-3- carboxylate (15.0 g, 50.7 mmol) (Gharat, al., WO 2013/118071), 3,5-dichlorobenzene boronic acid (11.6 g, 60.8 mmol), potassium carbonate (14.0 g, 101 mmol) 1,1-bis(diphenylphosphino)ferrocene-palladium(l l)dichloride dichloromethane complex (1 .24 g,1.52 mmol) and a degassed 5:1 mixture of dioxan and water (190 ml). The suspension was stirred overnight at 7000. Then an aqueous solution of sodium hydroxide (5 M, 101 ml, 505 mmol) was added and the dark mixture was refluxed for 6 h. Subsequently, hot water (110 ml), methanol (70 ml) and charcoal (2.5 g) were added and refluxing continued for a few minutes.The mixture was filtered hot and the filter cake washed with methanol / water (1:1). 5 M acetic acid (150 ml, 750 mmol) was added slowly under stirring to the hot filtrate to achieve a pH range of 6-7. Further 90 ml of water were added and the solvents were partially removed under reduced pressure. The suspension was cooled under stirring to RT and lateron to 0C. The precipitate was filtered off, washed with methanol / water (2:1), stirred in MTBE, filtered offagain and dried in vacuo.Yield: 17.5 g (92% purity, 95% of th.)LC-MS (Method Li): R1 = 1 .02 mm; MS (ESIpos): m/z = 334 [M+H]1HNMR Peaklist (400 MHz, DMSO-d6) 6 [ppm]: -0.008 (1.06), 0.008 (0.98), 1.909 (9.53),2.524 (1.24), 2.670 (0.41), 3.162 (0.87), 3.175 (0.89), 3.568 (5.51), 7.609 (2.04), 7.628 (3.44),7.650 (15.61), 7.654 (16.00), 7.769 (2.83), 7.773 (4.62), 7.778 (2.66), 7.788 (3.38), 7.791 (3.46), 7.806 (2.84), 7.809 (2.66), 7.874 (0.44), 7.879 (0.42), 7.948 (0.51), 7.952 (0.48), 8.364 (3.52), 8.368 (3.54), 8.385 (3.50), 8.388 (3.26), 8.603 (10.14), 12.202 (1.00).

Reference： [1]Patent: WO2018/87036,2018,A1 .Location in patent: Page/Page column 147; 148

77
[ 461-89-2 ]
[ 67492-50-6 ]
[ 57715-70-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	With pyridine; oxygen; copper diacetate; In N,N-dimethyl-formamide; at 20℃; for 2h;Catalytic behavior;	General procedure: To a solution of <strong>[461-89-2]6-azauracil</strong> (100 mg, 0.88 mmol) inDMF (10.0 mL) was added base (1.76 mmol) and Cu(OAc) 2(159 mg, 0.88 mmol) at room temperature. The resulting reationmixture was degassed with oxygen for 10 min and then addedarylboronic acids (0.96 mmol) at room temperature and stirredat appropriate temperature (Table-1) under oxygen atmosphere.The reaction mixture was diluted with water (15 mL) andextracted with dichloromethane (3 × 15 mL). The organic layerwashed with H 2 O (15 mL), brine solution (15 mL), dried overNa 2 SO 4 and concentrated. The obtained crude product waspurified by column chromatography (0 to 10 % CH 3 OH/CH 2 Cl 2 )to afford the title compounds. Spectral data for compounds 3a-r2-(3,5-Dichlorophenyl)-<strong>[461-89-2]1,2,4-triazine-3,5(2H,4H)-dione</strong>(3a) [22]: Off white solid; m.p.: 142-147 C; 1 H NMR (300MHz, DMSO-d 6 ) delta 12.75 (s, 1H), 7.76-7.75 (m, 1H), 7.65 (s,1H), 7.557 (s, 1H), 7.551 (s, 1H); 13 C NMR (100 MHz, DMSO-d 6 ) delta 155.7, 148.4, 135.0, 134.1, 132.6, 130.2, 128.50,128.25, 127.12; HRMS (ESI) m/z: calcd. for C 9 H 5 N 3 O 2 Cl 2[M+H] + 256.9754, found 256.9748; Anal. Calcd. C 9 H 5 N 3 O 2 Cl 2 :C, 41.89; H, 1.95; N, 16.28; Found: C, 41.86; H, 1.98; N,16.25.

Reference： [1]Asian Journal of Chemistry,2018,vol. 30,p. 2495 - 2501

78
[ 273-53-0 ]
[ 67492-50-6 ]
[ 172944-87-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; at 100℃; for 9.5h;Green chemistry;	General procedure: A mixture of benzoxazole (1mmol), aryl boronic acid(1 mmol), K2CO3(2mmol) and MNPFemBenzNHCNi complex (7) (100mg) in xylene (5mL) was stirred at100°C. The progress of reaction was monitored by TLC.After completion of reaction, 7 was separated by usingexternal magnet. Evaporation of solvent in vaccuo followedby column chromatography over silica gel using petroleumether/ethyl acetate aforded pure products. The productswere identified by FT-IR, 1H NMR, 13C NMR and mass

Reference： [1]Catalysis Letters,2018,vol. 148,p. 3178 - 3192

79
7-bromo-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-3-isopropyl-6-methylpyrazolo[5,1-b][1,3]thiazole-2-carboxamide [ No CAS ]
[ 67492-50-6 ]
7-(3,5-dichlorophenyl)-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-3-isopropyl-6-methyl-pyrazolo[5,1-b][1,3]thiazole-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66.1%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 100℃; for 0.666667h;Inert atmosphere; Microwave irradiation;	A microwave tube was charged with 3 niL dioxane, 7-bromo-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-3- isopropyl-6-methylpyrazolo[5,l-b][l,3]thiazole-2-carboxamide (150 mg, 0.34 mmol), 3,5- dichlorophenyl boronic acid (54.9 mg, 0.28 mmol), aqueous 2M sodium carbonate solution (1.44 mL) and (l,r-bis(diphenylphosphino)-ferrocene-palladium-dichloromethane complex (21 mg, 0.02 mmol). The reaction mixture was degassed with argon for 5 min and was treated in a microwave device (Biotage) for 40 min at 100 °C. The crude mixture was filtered and washed through a silica gel / sodium sulfate cartridge. The solvents of the filtrate were evaporated under reduced pressure; the remaining raw material was purified by flash column chromatography using a cyclohexane / ethyl acetate gradient to obtain the title compound as an off- white solid. Yield: 92.6 mg (0.185 mmol, 66.1 percent of th. regarding the boronic acid) LC-MS (Method L0): Rt = 1.93 min; MS (ESIpos): m/z = 500.0; 501.9 [M+H]+. -NMR (399,95) MHz, DMSO-d6) delta [ppm]: 8.92 (d, 1H, NH), 7.53 (s, 1H), 7.46 (s, 2H), 7.21 - 7.15 (m, 2H), 6.91 (t, 1H), 6.81 (d, 1H), 5.26 - 5.21 (q, 1H), 4.32 - 4.19 (m, 3H), 2.56 (s, 3H), 2.12 - 2.06 (m, 2H), 1.51 (d, 6H).

Reference： [1]Patent: WO2018/197401,2018,A1 .Location in patent: Page/Page column 110

80
[ 176199-35-2 ]
[ 67492-50-6 ]
(R)-2-((tert-butoxycarbonyl)amino)-3-(3',5'-dichloro-[1,1'-biphenyl]-4-yl)propanoic acid [ No CAS ]

Reference： [1]MedChemComm,2018,vol. 9,p. 1818 - 1825

81
methyl 4-iodo-6H-thieno[2,3-b]pyrrole-5-carboxylate [ No CAS ]
[ 67492-50-6 ]
methyl 4-(3,5-dichlorophenyl)-6H-thieno[2,3-b]pyrrole-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,4-dioxane; water; at 90℃;	Methyl 4-iodo-6H-thieno[2, 3-b]pyrrole-5-carboxylate (50 mg, 0.16 mmol) and 3,5-dichlorophenylboronic acid (37 mg, 0.19 mmol) were dissolved in a deoxygynated water: 1 ,4-dioxane (1:9, 1.5 mL). Bis(triphenylphosphine)palladium(l I) dichloride (5.7 mg, 0.01 mmol) and sodium carbonate (36 mg, 0.34 mmol) was then added. The vial was capped and heated to 90 °C overnight. The mixture was diluted with water (15 mL) and extracted with ethyl acetate (2x15 mL). The combined organic layers were dried with MgSO4, filtered and concentrated by rotary evaporation. The residue was purified by silica gel flash chromatography (20percent ethyl acetate in iso-hexane) to give the titled compounds as pale yellow solid, (35 mg, 66percent yield). ESI-MS [M-H] 324, 326; 1H NMR (400 MHz, CDCI3) O 9.31 (br s, NH), 7.51 (d, J = 1.9 Hz, 2H), 7.34 (t, J = 1.9 Hz, 1 H), 7.02 ?6.97 (m, 2H), 3.84 (5, 3H).

Reference： [1]Patent: WO2018/215800,2018,A1 .Location in patent: Paragraph 00189

82
[ 21193-80-6 ]
[ 67492-50-6 ]
4-amino-5-(3,5-dichlorophenyl)-N7-(β-D-ribofuranosyl)-pyrrolo[2,3-d]pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
28%	With trisodium tris(3-sulfophenyl)phosphine; palladium diacetate; sodium carbonate; In water; acetonitrile; at 100℃;Inert atmosphere;	General procedure: 31 (1 eq.), boronic acid (1.5 eq.) or pinacol ester [for compound14 (1.5 eq.)], Na2CO3 (9 eq.), Pd(OAc)2 (0.05 eq.) and TPPTS (0.15 eq.)were added to a 10mL round-bottom flask, equipped with a stir bar.Next, the flask was evacuated and refilled with argon. This procedure was repeated three times in total. Next, degassed MeCN(2 mL/mmol SM) and H2O (4 mL/mmol SM) were added to the solids under argon. After 5 min of stirring, the mixture was heatedto 100 C in a pre-heated oil bath. When the starting material was fully consumed (usually 1e3 h), the mixture was cooled to ambient temperature, and neutralized (pH ~ 7) with 0.5M aq. HCl. Themixture was evaporated till dryness, resuspended in MeOH and evaporated (three times). Next, the mixture was adsorbed onto Celite (fromMeOH) and eluted over a short silica pad (~5 cm) with 20% MeOH/DCM. The liquid was evaporated in vacuo and purified by column chromatography.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 164,p. 689 - 705

83
[ 103068-20-8 ]
[ 67492-50-6 ]
C₂₄H₁₆Cl₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In tetrahydrofuran; water; at 70℃; for 4h;	5'-Bromo-1,1': 3',1"-terphenyl (150 g, 85.1 mmol), <strong>[67492-50-6](3,5-dichlorophenyl)boronic acid</strong> (111.08 g, 582.1 mmol)Pd(PPh3)4 (28.03 g, 24.3 mmol), NaOH (58.21 g, 1455.3 mmol)THF (1.7 L) / H 2 O (0.9 L).Thereafter, the mixture is heated under reflux at 70 ° C for 4 hours. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was recrystallized from methylene chloride and hexane to obtain the product Sub 1-1-1 (143.80 g, 79percent).

Reference： [1]Patent: KR2019/269,2019,A .Location in patent: Paragraph 0105-0107

84
[ 239137-39-4 ]
[ 67492-50-6 ]
4-(3,5-dichlorophenyl)pyridin-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With potassium fluoride; tris-(dibenzylideneacetone)dipalladium(0); tri tert-butylphosphoniumtetrafluoroborate; In tetrahydrofuran; water; at 60℃;	4-Bromopyridin-3 -amine, 2.00 g (11.6 mmol), 3,5-dichlorophenylboronic acid, 3.30 g (17.3 mmol), tris(dibenzylideneacetone)dipalladium, 265 mg (0.3 mmol), tri-tert-butylphosphine tetrafluoroborate, 168 mg (0.6 mmoll), and potassium fluoride, 2.00 g (34.7 mmol), were dissolved in 16 mL of tetrahydrofuran and 4 mL of water. The mixture was stirred at 60 °C overnight. The solvent was removed in vacuo. Water was added, the mixture was extracted with ethyl acetate and the combined organic phases were dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel column chromatography (dichloromethane / methanol = 20: 1) to give 2.96 g (91percent) of the product as a yellow solid. LC-MS (Method Ml 6): Rt = 0.74 min; m/z = 239 (M+l)+.

Reference： [1]Patent: WO2019/2132,2019,A1 .Location in patent: Page/Page column 154

85
8-bromo-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-4-(dimethylamino)cinnoline-3-carboxamide [ No CAS ]
[ 67492-50-6 ]
8-(3,5-dichlorophenyl)-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-4-(dimethylamino)cinnoline-3-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In 1,4-dioxane; water; at 60℃; for 4h;Inert atmosphere;	A stirred mixture of 8-bromo-N-[(4S)-3,4-dihydro-2H-chromen-4-yl]-4-(dimethylamino)cinnoline-3- carboxamide (65 mg, 0.15 mmol), <strong>[67492-50-6](3,5-dichlorophenyl)boronic acid</strong> (32 mg, 0.17 mmol) and sodium carbonate (32 mg, 0.30 mmol) in 1,4-dioxane (1 mL) and water (0.15 mL) was sparged with nitrogen. [l, -Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (7 mg, 0.01 mmol) was added and the resulting mixture was stirred at 60 °C for 4 hours under nitrogen atmosphere in a closed vessel. The reaction mixture was cooled to room temperature and was concentrated in vacuo. Purification by flash column chromatography (gradient heptane / 5percent-100percent ethyl acetate) afforded 68 mg (0.14 mmol, 91percent of theory) of the title compound. LC-MS (Method L4): Rt = 3.51 min; m/z = 493/495 (M+l)+. *H NMR (400 MHz, DMSO-d6) delta 9.23 (d, J = 8.4 Hz, 1H), 8.29 (dd, J = 8.6, 1.2 Hz, 1H), 7.93 (dd, J = 7.1, 1.2 Hz, 1H), 7.83 (dd, J = 8.6, 7.1Hz, 1H), 7.76 - 7.67 (m, 3H), 7.36 (d, J = 7.6 Hz, 1H), 7.22 - 7.1 1 (m, 1H), 6.97 - 6.89 (m, 1H), 6.80 (dd, J = 8.2, 1.0 Hz, 1H), 5.33 (q, J = 6.0 Hz, 1H), 4.29 (q, J = 6.6, 6.1Hz, 2H), 3.17 (s, 6H), 2.27 - 2.15 (m, 1H), 2.15 - 2.02 (m, 1H).

Reference： [1]Patent: WO2019/2132,2019,A1 .Location in patent: Page/Page column 173

86
[ 39856-58-1 ]
[ 67492-50-6 ]
2-(3,5-dichlorophenyl)pyridin-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With potassium fluoride; tris-(dibenzylideneacetone)dipalladium(0); tri tert-butylphosphoniumtetrafluoroborate; In tetrahydrofuran; water; at 60℃;	2-Bromopyridin-3 -amine, 2.00 g (1 1.6 mmol), 3,5-dichlorophenylboronic acid, 3.30 g (17.3 mmol), tris(dibenzylideneacetone)dipalladium, 0.50 g (0.6 mmol), tri-tert-butylphosphine tetrafluoroborate, 0.30 g (1.2 mmol), and potassium fluoride, 2.00 g (34.7 mmol), were dissolved in 80 mL of tetrahydroiuran and 20 mL of water. The mixture was stirred at 60 C overnight. The solvent was removed in vacuo. Water was added, the mixture was extracted with ethyl acetate and the combined organic phases were dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10: 1) to give 1.40 g (51%) of the product as a yellow solid. LC-MS (Method M34): Rt = 0.77 min; m/z = 239 (M+l)+.

Reference： [1]Patent: WO2019/2132,2019,A1 .Location in patent: Page/Page column 134

87
[ 64318-28-1 ]
[ 67492-50-6 ]
tert-butyl (4-(3,5-dichlorophenoxy)phenethyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With pyridine; copper diacetate; In dichloromethane; at 20℃;Molecular sieve;	To a solution of (3,5-dichlorophenyl)boronic acid (380 mg; 2.00 mmol) and N-Boc-tyramine (237 mg; 1.00 mmol) in DCM ( 15.0 ml), was added copper(II) acetate ( 1 82 mg; 1.00 mmol), 4 A molecular sieves ( 100 mg), and pyridine (0.400 ml, 4.96 mmol), and the reaction mixture was stirred overnight at room temperature with the flask open. The reacton mixture was filtered, the filtrate was concentrated, and the crude material was subjected to flash column chromatography on silica gel, eluting with 0-30% ethyl acetate in hexane, to afford /ert-butyl (4-(3,5-dichlorophenoxy)phenethyl)carbamate as a white solid (320 mg; 0.838 mmol; 84% yield).

Reference： [1]Patent: WO2019/173507,2019,A1 .Location in patent: Page/Page column 22; 23

88
[ 13195-50-1 ]
[ 67492-50-6 ]
2-(3,5-dichlorophenyl)-5-nitrothiophene [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019

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CAS No. :	67492-50-6	MDL No. :	MFCD00051935
Formula :	C₆H₅BCl₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DKYRKAIKWFHQHM-UHFFFAOYSA-N
M.W :	190.82	Pubchem ID :	2734331
Synonyms :

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	2.0
Molar Refractivity :	46.29
TPSA :	40.46 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.99 cm/s

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.08
Log Po/w (WLOGP) :	0.67
Log Po/w (MLOGP) :	1.48
Log Po/w (SILICOS-IT) :	0.57
Consensus Log Po/w :	0.96

[ CAS No. 67492-50-6 ] {[proInfo.proName]}

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[ 67492-50-6 ] Synthesis Path-Upstream 1~7

[ 67492-50-6 ] Synthesis Path-Downstream 1~88

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[ 67492-50-6 ]

Organoboron

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

Log S (ESOL) :	-2.67
Solubility :	0.407 mg/ml ; 0.00213 mol/l
Class :	Soluble
Log S (Ali) :	-2.56
Solubility :	0.526 mg/ml ; 0.00276 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.52
Solubility :	0.572 mg/ml ; 0.003 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.94

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:

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

[ CAS No. 67492-50-6 ] {[proInfo.proName]}

Quality Control of [ 67492-50-6 ]

Related Doc. of [ 67492-50-6 ]

Product Details of [ 67492-50-6 ]

Calculated chemistry of [ 67492-50-6 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 67492-50-6 ]

Application In Synthesis of [ 67492-50-6 ]

[ 67492-50-6 ] Synthesis Path-Upstream 1~7

[ 67492-50-6 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 67492-50-6 ]

Organoboron

Aryls

Chlorides

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 67492-50-6 ]