[ CAS No. 1020174-04-2 ]

Name: 1020174-04-2|1-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole|97%
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Product Details of [ 1020174-04-2 ]

CAS No. :	1020174-04-2	MDL No. :	MFCD04114000
Formula :	C₁₀H₁₇BN₂O₂	Boiling Point :	308.3°C at 760 mmHg
Linear Structure Formula :	-	InChI Key :	N/A
M.W :	208.07 g/mol	Pubchem ID :	2760077
Synonyms :

Safety of [ 1020174-04-2 ]

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:

Application In Synthesis of [ 1020174-04-2 ]

Upstream synthesis route of [ 1020174-04-2 ]
Downstream synthetic route of [ 1020174-04-2 ]

[ 1020174-04-2 ] Synthesis Path-Upstream 1~6

1
[ 844501-71-9 ]
[ 74-88-4 ]
[ 1020174-04-2 ]
[ 847818-74-0 ]

Reference： [1] Patent: US2012/316166, 2012, A1, . Location in patent: Page/Page column 71

2
[ 151049-87-5 ]
[ 73183-34-3 ]
[ 1020174-04-2 ]

Yield	Reaction Conditions	Operation in experiment
44.19%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂; potassium acetate In 1,4-dioxane at 95℃; for 5 h; Inert atmosphere	Intermediate 702: 1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole Compound 701 (0.2 g, 1.24 mmol) was dissolved in 5 ml of 1,4-dioxane, added with 0.378 g (1.49 mmol) of bis(pinacolato)diboron, 0.365 g (3.72 mmol) of potassium acetate, and 0.11 g (0.124 mmol) of [1,1-bis(di-phenylphosphino)ferrocene]palladium chloride dichloromethane complex under the protection of nitrogen, heated to 95 °C and reacted for 5 h, and then cooled to room temperature. 15 mL of water was added, stirred for 1 h, and filtered to afford 0.114 g of solid. Yield: 44.19percent.

Reference： [1] Patent: EP3072893, 2016, A1, . Location in patent: Paragraph 0394; 0395
[2] Patent: EP2818473, 2014, A1, . Location in patent: Paragraph 0578

3
[ 61676-62-8 ]
[ 92525-10-5 ]
[ 1020174-04-2 ]

Yield	Reaction Conditions	Operation in experiment
54%	With n-butyllithium In tetrahydrofuran at -65 - -50℃; for 2 h; Inert atmosphere; Large scale	The compound 3-iodo-1-methyl-1H-pyrazole (2000 g, 9.6 mol, 1.0 eq)Was dissolved in 8 L of dry tetrahydrofuran,Then, Isopropoxyboronic acid pinacol ester (2146.1 g, 11.5 mol, 1.2 eq) was added to the solution,The solution was cooled to -65 to -50 ° C,Under argon protection,Was added dropwise n-butyllithium (6.25L, 12.5mol, 1.3eq),After completion of the dropwise addition, the reaction was stirred for 2 h at this low temperature,An aqueous solution of hydrochloric acid (1 mol / L) was added to the reaction solution to quench the reaction,The reaction solution was extracted three times with ethyl acetate,The combined organic layers were dried over saturated brine and the organic phase was concentrated. 1-methyl-1H-pyrazol-3-boronic acid pinacol ester(1080.9 g, 0.24 mol),Yield 54.0percentPurity 97percent +.

Reference： [1] Patent: CN105669733, 2016, A, . Location in patent: Paragraph 0037; 0038; 0039; 0040

4
[ 269410-08-4 ]
[ 74-88-4 ]
[ 1020174-04-2 ]

Reference： [1] Patent: WO2010/75270, 2010, A1, . Location in patent: Page/Page column 137

5
[ 844501-71-9 ]
[ 74-88-4 ]
[ 1020174-04-2 ]

Reference： [1] Patent: WO2018/13867, 2018, A1, . Location in patent: Paragraph 684

6
[ 844501-71-9 ]
[ 74-88-4 ]
[ 1020174-04-2 ]
[ 847818-74-0 ]

Reference： [1] Patent: US2012/316166, 2012, A1, . Location in patent: Page/Page column 71

[ 1020174-04-2 ] Synthesis Path-Downstream 1~24

1
(4-(7-bromo-5-chloro-8-methoxy-quinazolin-2-ylamino)phenyl)(morpholin-4-yl)methanone [ No CAS ]
[ 1020174-04-2 ]
(4-(5-chloro-8-methoxy-7-(1-methyl-1H-pyrazol-4-yl)-quinazolin-2-ylamino)phenyl)morpholin-4-yl-methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,2-dimethoxyethane; at 120℃; for 0.166667h;Microwave irradiation;	Step 4. Preparation pf N-(5-chloro-8-methoxy-7-(l-methyl-lH-pyrazol-4-yl)quinazolin-2- yl)morpholine-4-carboxatnideTo (4-(7-bromo-5-chloro-8-methoxyquinazolin-2-ylamino)phenyl) (morpholino)methanone (leq) in DME and 2M sodium carbonate solution was added l-methyl-3-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)-lH-pyrazole (3eq) and Pd^pPf)2Cl2-CH2Cl2 (0.05eq) and the mixture was micro waved for 10 min at 12O0C. The reaction mixture was then partitioned between ethyl acetate and water. The organic layer was concentrated and purifedon prep HPLC to yield N-(5- chloro-8-methoxy-7-( 1 -methyl- 1 H-pyrazol-4-yl) quinazolin-2-yl)mophiholine-4-carboxamide. ES/MS m/z 479(MH+).

Reference： [1]Patent: WO2007/117607,2007,A2 .Location in patent: Page/Page column 348

2
[ 1020174-04-2 ]
[ 953039-95-7 ]
7-(1-methyl-1H-pyrazol-4-yl)-N-(4-(morpholine-4-sulfonyl)-phenyl)-quinazolin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,2-dimethoxyethane; at 120℃; for 0.166667h;Microwave irradiation;	Step 2. Preparation of 7-(l -methyl- lH-pyrazol-4-yl) -N- (4-(motaupholinosulfonyl) phenyl)quinazolin-2-amineTo a solution of 2-(4-(mophiholinosulfonyl)phenylamino) quinazolin-7-yltrifluoromethane sulfonate (leq) in DME was added 2M sodium carbonate solution and l-methyl-4-(4,4,5,5,- tetramethyl-ls3,2-dioxaborolan-2-yl)-lH-pyrazole (3eq) and Pd (dppf)2Cl2.CH2Cl2 (0.05eq) and the mixture was micro waved for 10 min at 1200C. The reaction mixture was then partitioned between ethyl acetate and water. The organic layer was washed with brine, dried, concentrated and purified by semi-preparative HPLC to provide 7-(l -methyl- lH-pyrazol-4-yl) -N- (4- (morpholinosulfonyl) phenyl) quinazolin-2-amine in 60%yield. ES/MS m/z 551.1(MH+).

Reference： [1]Patent: WO2007/117607,2007,A2 .Location in patent: Page/Page column 352

3
[ 1020174-04-2 ]
[ 1041861-97-5 ]
[ 1020173-14-1 ]

Yield	Reaction Conditions	Operation in experiment
56%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; at 100℃; for 16h;Inert atmosphere;	A solution of Example A23 (3 g, 12.6 mmol), l-methyl-3- (4,4,5, 5-tetramethyl-[l,3,2]dioxaborolan-2-yl)-lH-pyrazole (5.2 g, 25.2 mmol), and Na2C03 (2.7 g, 25.2 mmol) in DME (18 mL) and water (6 mL) was sparged with nitrogen for 20 min. Pd(PPh3)4 (729 mg, 0.63 mmol) was added and the resulting mixture was heated to 100 C for 16 h. The solvent was removed under reduced pressure and the crude product was suspended in water and extracted with EtOAc. The organic layer was washed with brine, dried (Na2SC>4), concentrated in vacuo and purified by silica gel chromatography to give 2-fiuoro-4-(2-(l -methyl- 1 H-pyrazol-4-yl)pyridin-4- yloxy)aniline (2 g, 56% yield). 1H NMR (300 MHz, DMSO-i/6) delta 8.31 (d ,J = 5.7 Hz, 1 H), 8.21 (s, 1 H), 7.92 (s, 1 H), 7.12 (s, J = 2.4 Hz, 1 H), 6.96 (m, 1 H), 6.85-6.72 (m, 2 H), 6.56 (m, 1 H), 5.15 (s, 2 H), 3.84 (s, 3H); MS (ESI) m z: 285.0 (M+H+)
56%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; at 100℃; for 16.33h;Inert atmosphere;	A solution of 4-(2-chloropyridin-4-yloxy)-2-fluorobenzenamine (3 g, 12.6 mmol), <strong>[1020174-04-2]1-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrazole</strong> (5.2 g, 25.2 mmol), and Na2CO3 (2.7 g, 25.2 mmol) in DME (18 mL)/water (6 mL) was sparged with nitrogen for 20 min. Pd(PPh3)4 (729 mg, 0.63 mmol) was added and the resulting mixture was heated to 100 C. for 16 h. The solvent was removed under reduced pressure and the crude product was suspended in water and extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4, concentrated in vacuo and purified via silica gel chromatography to give 2-fluoro-4-((2-(1-methyl-1H-pyrazol-4-yl)pyridin-4-yl)oxy)aniline (2 g, 56% yield). 1H NMR (300 MHz, DMSO-d6): delta 8.31 (d, J=5.7 Hz, 1H), 8.21 (s, 1H), 7.92 (s, 1H), 7.12 (d, J=2.4 Hz, 1H), 6.96 (m, 1H), 6.85-6.72 (m, 2H), 6.56 (m, 1H), 5.15 (s, 2H), 3.84 (s, 3H); MS (ESI) m/z: 285.0 (M+H+).

Reference： [1]Patent: WO2013/36232,2013,A2 .Location in patent: Paragraph 00259
[2]Patent: US2014/315917,2014,A1 .Location in patent: Paragraph 0514

4
[ 269410-08-4 ]
[ 74-88-4 ]
[ 1020174-04-2 ]

Yield	Reaction Conditions	Operation in experiment
		Step 1: l-Methyl-3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolcm-2-yl)-lH-pyrazole; N O Potassium tert-butoxide in THF (1.0 M, 0.309 mL, 0.309 mmol) was added to a solution of 3- (4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2-yl)-lH-pyrazole (30.0 mg, 0.155 mmol, Alfa Aesar, Cat. No. H27619) in DMF (0.5 mL) and stirred at r.t. for 10 min, and then methyl iodide (28.9 uL, 0.464 mmol) was added and the stirred at r.t. for 1 h. LCMS showed the reaction was complete. The mixture was diluted with ethyl acetate, washed with water and brine, dried over Na2SCu, filtered, and concentrated to give the crude product which was directly used in the next reaction without further purification. LCMS (M+H-82)+: m/z = 127.2.

Reference： [1]Patent: WO2010/75270,2010,A1 .Location in patent: Page/Page column 137

5
[ 1020174-04-2 ]
4-(7-bromo-3-methyl-3,4-dihydroisoquinolin-2(1H)-yl)-6-(4-methylpiperazin-1-yl)pyrimidin-2-amine [ No CAS ]
4-[3-methyl-7-(1-methyl-1H-pyrazol-3-yl)-3,4-dihydroisoquinolin-2(1H)-yl]-6-(4-methylpiperazin-1-yl)pyrimidin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;bis(di-tert-?butyl(4-?dimethylaminophenyl)?phosphine)?dichloropalladium(II); In 1,4-dioxane; water; at 90℃;Inert atmosphere;	Step 2: 4-[3-Methyl- 7 -(I -methyl- lH-pyrazo/-3-yl)-3, 4-dihydroisoquinolin-2(lH)-yl]-6-(4- methylpiperazin-l-yl)pyrimidin-2-amim; A mixture of l-methyl-3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-. H-pyrazole ( l 1.5 mg, 0.0518 mmol), 4-(7-bromo-3-methyl-3,4-dihydroisoquinolin-2(l H)-yl)-6-{4-methylpiperazin-l- yl)pyrimidin-2-amine (0.018 g, 0.043 mmol) (Peak 1, Example 49, Step 7). dichloro(bis{di-tert-butyl[4- (dimethylamino)phenyl]phosphoranyl})palladium (0.916 mg, 0.00129 mmol), and sodium carbonate (9.14 mg, 0.0862 mmol) in 1,4-dioxane (0.50 mL) and water (0.10 mL) was vacuumed and refilled with N2 for 3 times and then stirred at 90 0C overnight. The mixture was purified by RP-HPLC (pH = 10) to afford the desired product. LCMS (M+H)+: m/z = 419.3 .

Reference： [1]Patent: WO2010/75270,2010,A1 .Location in patent: Page/Page column 137-138

6
[ 1020174-04-2 ]
[ 1263185-81-4 ]
9-tert-butyl-2-(1-methyl-pyrazol-3-yl)-3-methoxy-13-(2-thienyl)-5,6,9,10,11,12-hexahydro-8H-azepino[4',3':4,5]pyrrolo[2,1-a]isoquinolin-8-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With water; potassium carbonate; In 1,2-dimethoxyethane; at 150℃; for 1h;Inert atmosphere; Microwave irradiation;	9-tert-butyl-2-((1-methyl-pyrazol)-3-yl)-3-yl)-3-methoxy-13-(2-thienyl)-5,6,9,10,11,12-hexahydro-8H-azepino[4',3':4,5]pyrrolo[2,1-a]isoquinolin-8-one (4h) A solution of 67 mg of 4e, 55 mg of K2CO3 and 56 mg of 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-1H-pyrazole in 3 ml of degassed 90% aq. dimethoxyethane was heated in a microwave oven under N2 atmosphere for 1 hr at 150 C. The reaction mixture was diluted with water and the product was extracted into ethyl acetate. The organic layer was washed, dried, concentrated and the product was purified by preparative HPLC, using a gradient of CH3CN-water. The product fractions were pooled and freeze-dried, to give 17 mg of 4h. MS-ESI: [M+1] 501.4. NMR (CDCl3) delta 1.53 (s, 9, tertC4H9), 1.90 (m, 2, CH2), 2.60, 3.16, 3.44 and 5.51 (4t, 8, 4CH2) 3.88 and 3.90 (2s, 6, N-CH3+OCH3), 6.77 and 7.63 (2s, 2, Ar-H), 7.28 and 7.34 (2s, 2, pyrazole-H), 6.98, 7.18 and 7.45 (3m, 3, thiophene-H).

Reference： [1]Patent: US2011/28450,2011,A1 .Location in patent: Page/Page column 18

7
[ 1020174-04-2 ]
(1r,4r)-2-methoxyethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-3-(6-chloropyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-(2-methoxyethoxy)cyclohexanecarboxylate [ No CAS ]
(1r,4r)-2-methoxyethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-3-(6-(1-methyl-1H-pyrazol-3-yl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-(2-methoxyethoxy)cyclohexanecarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate monohydrate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; water; at 150℃; for 16h;Inert atmosphere;	( 1 r,4r)-2~methoxyethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-3 -(6- chloropyridin-3 -yl)pyrazolo [ 1 ,5-a]pyrimidin-5-yl)- 1 -(2- methoxyethoxy)cycIo exanecarboxylate (627 mg, 0.82 mmol) in dioxane (8 mL) and water (1 mL) was treated with boronate (256.4 g, 1.23 mmol), Pd(dppf)Ci2.CH2Cl2 (68.14 mg, 0.082 mmol) and Kappa3RhoOmicron? (567.2 mg, 2.46 mmol) under argon and heated at 150C for 16 h. Upon cooling, the mixture was filtered through Celite and the filtrate was evaporated off under reduced pressure to give crude residue which was purified by column chromatography (Si02, 0· 40% hexane-EtOAc) to provide desired product (lr,4r)~2-methoxyethyl 4-(7-(bis((2- (trimethylsilyl)ethoxy)methyl)amino)-3 -(6-( 1 -methyl- 1 H-pyrazol-3-yl)pyridin-3- yl)pyrazolo[l ,5-a]pyrimidin-5-yl)-l~(2-methoxyethoxy)cyclohexanecarboxylate (696 mg). HPLC-MS tR-3.49 min (UV 25 nw). Mass calculated for formula C40H63N7O7Si2 809.43;observed MH+ (LCMS) 810.3 (m/z).

Reference： [1]Patent: WO2012/27234,2012,A1 .Location in patent: Page/Page column 70; 71

8
[ 844501-71-9 ]
[ 74-88-4 ]
[ 1020174-04-2 ]
[ 847818-74-0 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate; In acetonitrile; at 20℃; for 70h;	EXAMPLE 7Synthesis of Obtained [2-(1-methyl-1H-pyrazol-3-yl)-[1,8]naphthyridin-4-yl]-pyridin-4-yl-amine (no. 35) and [2-(2-Methyl-2H-pyrazol-3-yl)-[1,8]naphthyridin-4-yl]-pyridin-4-yl-amine (no. 36) To a solution of 10.6 g (54.7 mmol) <strong>[844501-71-9]3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrazole</strong> in 100 ml acetonitrile, 17.8 g (54.7 mmol) caesium carbonate were added and the mixture stirred at ambient temperature for 70 hrs. The reaction mixture was filtered and the residue washed with acetonitrile. The combined filtrates were evaporated and taken into tert.butylmethylether. Undissolved material was filtered off; the filtrate was dried over sodium sulfate and evaporated. One got a mixture of 1-methyl-<strong>[844501-71-9]3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrazole</strong> und 1-methyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrazole as colorless, slowly crystallizing oil.

Reference： [1]Patent: US2012/316166,2012,A1 .Location in patent: Page/Page column 71

9
[ 1020174-04-2 ]
[ 1426135-85-4 ]
[ 1426133-19-8 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 12h;Inert atmosphere;	Methyl 3-(3-(3-(7-bromoimidazo[1,2-a]pyridine-3-carboxamido)-4-methylphenyl)-1,2,4-oxadiazol-5-yl)azetidine-1-carboxylate (42) (40 mg, 0.078 mmol), <strong>[1020174-04-2]1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong> (19.6 mg, 0.094 mmol) and Pd(PPh3)4 (9 mg, 0.0078 mmol) were added to a flask equipped with a stir bar. The flask was evacuated and backfilled with nitrogen several times. DMF (1 mL) and 1.8 M K2CO3 (0.094 mmol) were added by syringe. The flask was sealed and heated at 80 C. for 12 hours. The reaction was filtered and directly purified by preparative reverse phase HPLC to afford methyl 3-(3-(4-methyl-3-(7-(1-methyl-1H-pyrazol-3-yl)imidazo[1,2-a]pyridine-3-carboxamido)phenyl)-1,2,4-oxadiazol-5-yl)azetidine-1-carboxylate (F56). MS m/z 513.2 (M+1)+.

Reference： [1]Patent: US2013/59832,2013,A1 .Location in patent: Paragraph 0564-0565

10
[ 1020174-04-2 ]
[ 1432514-99-2 ]
[ 1432513-62-6 ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; caesium carbonate; In 1,4-dioxane; water; at 90℃; for 24h;Sealed tube;	General procedure: Preparation of (i?)-5-Fluoro-3-(l-(3-(l-methyl-lH-pyrazol-3-yl phenyl)ethyl)-2-oxo-N-(1.2,4- thiadiazol-5-yl)-2,3-dihydrobenzof d1oxazole-6-sulfonamide (28-3)[0234] In a sealed vial, compound of Formula 28-2 (45 mg, 0.090 mmol), l-methyl-3-(4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrazole (21 mg, 0.10 mmol), PdC12(dppf)-CH2C12 adduct (7.3 mg, 0.009 mmol), and cesium carbonate (88 mg, 0.270 mmol) were combined in dioxane (1 mL) and water (0.14 mL). The mixture was heated at 90 C for 24 hours. The mixture was diluted with dioxane (4 mL), filtered through a celite pad, and the filtrate was concentrated. The resulting residue was purified by reverse phase HPLC (20-100% MeCN in water with 0.1% TFA, CI 8 column) to yield 28-3 as a white solid. ? NMR ? (ppm)(DMSO-d): 8.50 (s, 1 H); 7.74 (d, J = 5.6 Hz, 1 H); 7.63 (s, 1 H); 7.52-7.46 (m, 5 H); 7.41 (d, J = 9.8 Hz, 1 H); 6.40 (d, J = 1.9 Hz, 1 H); 5.65 (q, J = 7.2 Hz, 1 H); 3.79 (s, 3 H); 1.91 (d, J = 7.2 Hz, 3 H). LRMS C21H18FN604S2 [M+H] calc 501.08, obs 501.0.

Reference： [1]Patent: WO2013/63459,2013,A1 .Location in patent: Paragraph 0234

11
[ 1020174-04-2 ]
7-bromo-N-(5-(2-(2,6-cis-dimethylpiperidin-1-yl)ethylcarbamoyl)-2-fluorophenyl)imidazo[1,2-a]pyridine-3-carboxamide [ No CAS ]
[ 1426530-82-6 ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; caesium carbonate; In 1,2-dimethoxyethane; water; at 100℃; for 1h;Inert atmosphere; Microwave irradiation;	Example 1.10N-(5-(2-(2,6-cis-Dimethylpiperidin-1 -yl)ethylcarbamoyl)-2-fluorophenyl)-7-(1 - methyl-1 H-pyrazol-5-yl)imidazo[1 ,2-a]pyridine-3-carboxamidePdCI2(dppf).CH2CI2 adduct (39.5 mg, 0.048 mmol) was added to a mixture comprising 1 -methyl-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 H-pyrazole (commercially available) (212 mg, 1.017 mmol), 7-bromo-N-(5-(2-(2,6-cis- dimethylpiperidin-1 -yl)ethylcarbamoyl)-2-fluorophenyl)imidazo[1 ,2-a]pyridine-3- carboxamide (Intermediate 4C) (500 mg, 0.968 mmol), Cs2C03 (1262 mg, 3.87 mmol) in 1 ,2-dimethoxyethane (10 ml) and water (4.29 ml). The mixture was degassed thoroughly refilling with nitrogen (x3). The mixture was heated using microwave radiation at 100C for 1 hour. The water was removed by pipette and the organic portion was concentrated in vacuo. The residue was dissolved in MeOH and dry loaded onto silica. The crude product was purified by chromatography on silica eluting with 0-20% MeOH in DCM to afford the title compound. (See Table 1 for characterising data).

Reference： [1]Patent: WO2013/30802,2013,A1 .Location in patent: Page/Page column 80; 81

12
[ 1020174-04-2 ]
[ 1426530-70-2 ]
[ 1426530-94-0 ]

Yield	Reaction Conditions	Operation in experiment
		step 2: 4-Fluoro-3-[7-(2-methyl-2H-pyrazol-3-yl)-imidazo[1 ,2-a]pyridine-3-carbonyl]- amino}-benzoic acid3-[(7-Bromo-imidazo[1 ,2-a]pyridine-3-carbonyl)-amino]-4-fluoro-benzoic acid methyl ester (step 1 )(1200 g, 3.060 mol), 1-methyl-3-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)-1 H-pyrazole (commercially available) (764 g, 3.67 mol),PdCI2(dppf CH2Cl2 (75.0 g, 91.8 mmol) in dioxane (10 L) and aqueous Na2C03 (2 N, 4.6 L) were heated to reflux for 6 hr. The reaction mixture was cooled to 50 C and filtered. The filtrate was heated to reflux, to which was added AcOH (600 g, 10.0 mol) was added dropwise. During the course of addition solids came out of solution to give pale pink slurry. After addition the mixture was slowly cooled to RT and filtered. To the filter cake was added dioxane (20 L) followed by heating to reflux to obtain a solution. The solution was cooled to RTand filtered to provide the title compound as a white solid;1H NMR (400 MHz, DMSO-d6) delta 4.00 (s, 3 H) 6.67 (s, 1 H) 7.46 (t, J=9.41 Hz, 1 H) 7.40 (d, J=7.03 Hz, 1 H) 7.54 (s, 1 H) 7.85 (d, J=2.26 Hz, 1 H) 7.99 (s, 1 H) 8.28 (d, J=6.27 Hz, 1 H) 8.67 (s, 1 H) 9.47 (d, J=7.03Hz, 1 H) 10.35 (s, 1 H).Rt 5.40 mins; MS m/z 380.1 {M+H}+; Method 10 min LC

Reference： [1]Patent: WO2013/30802,2013,A1 .Location in patent: Page/Page column 81; 82

13
[ 1020174-04-2 ]
C₂₁H₂₀BrFN₄O₃ [ No CAS ]
C₂₅H₂₅FN₆O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium hydrogencarbonate; cesium fluoride; In 1,4-dioxane; water; at 120℃; for 0.333333h;Microwave irradiation;	Arylbromide 64a is prepared analogously to the procedure described in Example 63, Steps 1 , 3 and 4. In step 3, pyrazole 23f is used for the ketone formation. Compound 1043 is prepared using the conditions of general procedure D2, substituting K2C03 by NaHC03. Arylbromide 64a (90.0 mg, 0.13 mmol) is treated with 25a (83.9 mg, 0.40 mmol), NaHC03 (22.3 mg, 0.27 mmol) and CsF (60.6 mg, 0.40 mmol) and PdCI2dppf (10.9 mg, 0.013 mmol) in dioxane- H20 (4: 1 , 1.5 mL). The mixture is heated in the microwave at 120C for 20 min. The residue is purified by preparative HPLC to provide compound 1043.

Reference： [1]Patent: WO2013/91096,2013,A1 .Location in patent: Page/Page column 76

14
[ 1020174-04-2 ]
1-(3-bromo-1-trityl-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-[(1R)-1-phenylethyl]urea [ No CAS ]
(R)-1-(3-(1-methyl-1H-pyrazol-3-yl)-1-trityl-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-(1-phenylethyl)urea [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; at 80℃; for 1h;Inert atmosphere;	Step 2: (R)- 1 -(3 -bromo- 1 -trityl- 1 H-pyrazolo [4,3 -c]pyridin-6-yl)-3 -(1 -phenylethyl)urea (36 mg, 0.060 mmol), l-methyl-3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrazole (18.6 mg, 0.090 mmol), PdCl2(dppf)-CH2Cl2 adduct (7.3 mg, 8.96 muiotaetaomicron), 1,4-dioxane (0.6 mL) and Na2C03 (0.08 mL, 0.160 mmol, 2M) were charged in a vial. The mixture was evacuated and purged with nitrogen six times and heated at 80 C for lh. The mixture was diluted with EtOAc, washed with water, brine, dried (Na2S04) and concentrated in vacuo to afford crude (R)-l-(3-(l-methyl-lH-pyrazol-3-yl)-l^ phenylethyl)urea, which was used as such in the next step. MS ESI calcd. For C3gH34N70 [M + H]+ 604, found 604.
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; at 80℃; for 1h;Inert atmosphere;	R)-1-(3-bromo-1-trityl-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-(1-phenylethyl)urea (36 mg, 0.060 mmol), <strong>[1020174-04-2]1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong> (18.6 mg, 0.090 mmol), PdCl2(dppf)-CH2Cl2 adduct (7.3 mg, 8.96 mumol), 1,4-dioxane (0.6 mL) and Na2CO3 (0.08 mL, 0.160 mmol, 2M) were charged in a vial. The mixture was evacuated and purged with nitrogen six times and heated at 80 C for 1h. The mixture was diluted with EtOAc, washed with water, brine, dried (Na2SO4) and concentrated in vacuo to afford crude (R)-1-(3-(1-methyl-1H-pyrazol-3-yl)-1-trityl-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-(1-phenylethyl)urea, which was used as such in the next step. MS ESI calcd. For C38H34N7O [M + H]+ 604, found 604.

Reference： [1]Patent: WO2013/63214,2013,A1 .Location in patent: Page/Page column 115
[2]Patent: EP2770987,2018,B1 .Location in patent: Paragraph 0399

15
[ 1020174-04-2 ]
[ 1581258-29-8 ]
[ 1581258-02-7 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 150℃; for 1h;Microwave irradiation;	Example 7: V-(2-(2,2-dimethyl-4-phenyltetrahydro-2H-pyran-4-yl)ethyl)-6-(1- methyl-1 H-pyrazol-3-yl)pyrazin-2-amine 2M K2C03 solution (aq, 104 muIota_, 28.7 mg, 0.208 mmol) was added to a solution of the compound of 11 (30 mg, 0.087 mmol), methyl-pyrazole-4-boronic acid pinacol ester (C43)(Boron Molecular, CAS: 761446-44-0, CAT: BM103) (36 mg, 0.173 mmol) and fefra/c/s(triphenylphosphine)palladium(0) (5 mg, 0.004 mmol) in dioxane (0.5 mL) and heated to 150C under microwave irradiation for 1 h. The solution was then concentrated and resuspended in methanol before being loaded onto a silica SCX cartridge. The cartridge was washed with methanol and the desired product was eluted upon addition of 2M NH3 in MeOH. Further purification by silica column chromatography (4 g, DCM:MeOH 0-2%; stains - UV, Dragendorff) fractions 51-57 resulted in isolation of the product as a clear oil. (25.8 mg, 0.066 mmol, 76%). Fractions 58-62 were also collected however they contained a slight impurity. 1 H NMR (MeOD, 500 MHz) delta 7.945 (bs, 1 H, ArCH), 7.858 (bs, 1 H, ArCH), 7.813 (bs, 1 H, ArCH), 7.36-7.47 (m, 5H, ArCH), 7.25-7.30 (m, 1 H, ArCH), 3.949 (s, 3H, NCH3), 3.80-3.89 (m, 1 H, OCH2), 3.72-3.80 (m, 1 H, OCH2), 3.16-3.26 (m, 1 H, CH2), 2.86- 2.96 (m, 1 H, CH2), 2.51-2.59 (m, 1 H, CH2), 2.27 -2.36 (m, 1 H, CH2), 1.88-1.98 (m, 1 H, CH2), 1.65-1.77 (m, 3H, CH2), 1.187 (s, 3H, CH3), 0.669 (s, 3H, CH3), NH not observed. LCMS m/z C23H29N50 ES+ (RT: 5.05 min) 393.3 [MH+ + 1] (20%), 392.3 [MH+] (100%).

Reference： [1]Patent: WO2014/41349,2014,A1 .Location in patent: Page/Page column 59

16
[ 1020174-04-2 ]
[ 27048-04-0 ]
6-(1-methyl-1H-pyrazol-3-yl)-3-nitropyridin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 120℃; for 0.833333h;Inert atmosphere; Microwave irradiation;	a) 6-(1 -Methyl- 1H-pyrazol-3-yl)-3-nitropyridin-2-amine (A87) A mixture of 2-amino-3-nitro-6-chloropyridine A44 (0.20 g, 1.1 mmol), Na2C03 (0.489 g, 4.61 mmol), 1-methyl-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 --pyrazole A86 (0.312 g, 1.50 mmol) and PdCI2(dppf) DCM solvate (0.072 g, 0.086 mmol) in dioxane (9.5 ml_) and H20 (0.5 ml_) was degassed for 10 minutes under a stream of nitrogen. The mixture was irradiated in the microwave at 120 C for 50 minutes. The cooled mixture was evaporated under reduced pressure, then purified by silica gel chromatography (40 g silica cartridge, 0- 100% EtOAc in petroleum benzine 40-60 C) to give the title compound as a yellow solid (0.155 g, 61 %); H NMR (400 MHz, cf DMSO) delta 8.42 (d, J = 8.8 Hz, 1 H), 8.09 (br. s, 2H), 7.52 (d, J = 2.0 Hz, 1 H), 7.16 (d, J = 8.8 z, 1 H), 7.00 (d, J = 2.0 Hz, 1 H), 4.23 (s, 3H). LCMS-A: rt 5.63 min, m/z (positive ion) 220.1 [M+H]+.

Reference： [1]Patent: WO2014/128465,2014,A1 .Location in patent: Page/Page column 98

17
[ 1020174-04-2 ]
[ 1225278-68-1 ]
[ 1225278-37-4 ]

Yield	Reaction Conditions	Operation in experiment
1.062 g	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In water; N,N-dimethyl-formamide; at 90℃; for 4h;Inert atmosphere;	A solution of Example A21 (1.177 g, 4.31 mmol) and <strong>[1020174-04-2]1-methyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong> (1.166 g, 5.60 mmol) in DMF (16 mL) was treated with Cs2CO3 (4.21 g, 12.93 mmol) and water (5 mL), sparged with Ar, treated with Pd(PPh3)4 (0.249 g, 0.215 mmol) and heated at 90 C. for 4 h. The mixture was cooled to RT, diluted with 4:1 EtOAc/THF, washed with 10% LiCl (2), then brine (1), dried over MgSO4, evaporated under reduced pressure and purified via silica gel chromatography (EtOAc/Hex) to yield 5-chloro-2-fluoro-4-((2-(1-methyl-1H-pyrazol-4-yl)pyridin-4-yl)oxy)aniline as a tan solid (1.062 g, 77%). 1H NMR (400 MHz, DMSO-d6): delta 8.31 (d, 1H), 8.24 (s, 1H), 7.95 (s, 1H), 7.20 (d, 1H), 7.13 (d, 1H), 6.92 (d, 1H), 6.52 (dd, 1H), 5.49 (s, 2H), 3.84 (s, 3H); MS (ESI) m/z: 319.1 (M+H+).

Reference： [1]Patent: US2014/315917,2014,A1 .Location in patent: Paragraph 0317

18
[ 1020174-04-2 ]
2-bromo-6-(4-chlorophenyl)-1-isopropyl-5-(1-methyl-6-oxo-1,6-dihydropyridin-3-yl)-5,6-dihydropyrrolo[3,4-d]imidazol-4(1H)-one [ No CAS ]
6-(4-chlorophenyl)-1-isopropyl-2-(1-methyl-1H-pyrazol-3-yl)-5-(1-methyl-6-oxo-1,6-dihydropyridin-3-yl)-5,6-dihydropyrrolo[3,4-d]imidazol-4(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; caesium carbonate; In 1,4-dioxane; water; at 100℃; for 7h;Inert atmosphere;	To a solution of 2-bromo-6-(4-chlorophenyl)- 1 -isopropyl-5-(1 -methyl-6-oxo- 1 ,6-dihydropyridin-3- yl)-5,6-dihydropyrrolo[3,4-d]imidazol-4(1H)-one (Step 19.4) (100 mg, 0.22 mmol) in dioxane (2 mL) and water (0.2 mL) under nitrogen were added 1-methyl-5-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-1H-pyrazole (Step 21.1) (58.6 mg, 0.28 mmol), 052003 (183 mg, 0.563 mmol) and PdCI2(dppf).CH2CI2 adduct (26.5 mg, 0.03 mmol). The resulting mixture was flushed with Ar, heated up and stirred at 100 00 for 3 hr. The reaction was cooled down to RT, 1-methyl- 5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 H-pyrazole (43 mg) and PdCI2(dppf).CH2CI2 adduct (20 mg) were added and the resulting mixture was heated up and stirred at 100 00 for 105 mm. The reaction mixture was diluted with EtOAc and water and both phases were separated. The aq. layer was extracted twice with EtOAc. Combined extracts were washed with brine, dried over Na2504, filtered and concentrated under reduced pressure. The crude product was purified by preparative HPLC (gradient 5-100 % CH3CN in 20 mm) followed by basic workup and trituration in iPr2O to afford the title product (44 mg, 44 % yield) as pale beige crystals. tR: 0.82 mm (LC-MS 2); ESl-MS: 463 [M+H] (LC-MS 2).The title compound was prepared in analogy to the procedure described in Example 21 using 2- bromo-6-(4-chlorophenyl)- 1 -isopropyl-5-(1 -methyl-6-oxo- 1 ,6-dihydropyridin-3-yl)-5,6- dihydropyrrolo[3,4-d]imidazol-4(1 H)-one (Step 19.4) and 1-methyl-3-(4,4,5,5-tetramethyl-1 3,2- dioxaborolan-2-yl)-1H-pyrazole (Step 22.1) at 100 00 for 7 hr. tR: 0.87 mm (LC-MS 2); ESl-MS:463 [M+H] (LC-MS 2).

Reference： [1]Patent: WO2014/191894,2014,A1 .Location in patent: Page/Page column 92; 93

19
[ 151049-87-5 ]
[ 73183-34-3 ]
[ 1020174-04-2 ]

Yield	Reaction Conditions	Operation in experiment
44.19%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 95℃; for 5h;Inert atmosphere;	Intermediate 702: 1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole Compound 701 (0.2 g, 1.24 mmol) was dissolved in 5 ml of 1,4-dioxane, added with 0.378 g (1.49 mmol) of bis(pinacolato)diboron, 0.365 g (3.72 mmol) of potassium acetate, and 0.11 g (0.124 mmol) of [1,1-bis(di-phenylphosphino)ferrocene]palladium chloride dichloromethane complex under the protection of nitrogen, heated to 95 C and reacted for 5 h, and then cooled to room temperature. 15 mL of water was added, stirred for 1 h, and filtered to afford 0.114 g of solid. Yield: 44.19%.
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 120℃; for 3h;Microwave irradiation;	A mixture of 3-bromo-1-methyl-1H-pyrazole obtained in Step A (400 mg), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi-1,3,2-dioxaborolane (694 mg), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) (101 mg), potassium acetate (488 mg) and 1,4-dioxane (5.0 mL) was heated with microwave irradiation at 120C for 3 hr. The insoluble substance was removed by filtration, and the solvent was evaporated under reduced pressure to give the title compound as a crude product. 1H NMR (400 MHz, CDCl3) delta 1.27 (12H, s), 3.98 (3H, s), 6.66 (1H, d, J = 2.0 Hz), 7.38 (1H, d, J = 2.0 Hz).

Reference： [1]Patent: EP3072893,2016,A1 .Location in patent: Paragraph 0394; 0395
[2]Patent: EP2818473,2014,A1 .Location in patent: Paragraph 0578

20
[ 1020174-04-2 ]
3-amino-7-bromo-5-(3-methylbutan-2-yl)-1,5-dihydro-4H-pyrazolo[4,3-c]pyridin-4-one [ No CAS ]
3-amino-5-(3-methylbutan-2-yl)-7-(1-methyl-1H-pyrazol-3-yl)-1,5-dihydro-4H-pyrazolo[4,3-c]pyridin-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
36 mg	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; N,N-dimethyl-formamide; at 120℃; for 1h;Microwave irradiation;	A mixture of 3-amino-7-bromo-5-(3-methylbutan-2-yl)-1,5-dihydro-4H-pyrazolo[4,3-c]pyridin-4-one obtained in Step G (332 mg), <strong>[1020174-04-2]1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong> (347 mg), tetrakis(triphenylphosphine)palladium(0) (128 mg), aqueous sodium carbonate solution (2 M, 1.11 mL) and N,N-dimethylformamide (6.0 mL) was heated with microwave irradiation at 120C for 1 hr. The reaction mixture was cooled to room temperature, and poured into water, and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (methanol/ethyl acetate), and then HPLC (C18, mobile phase: water/acetonitrile (containing 0.1% TFA)). To the obtained fraction was added saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound (36.0 mg). 1H NMR (400 MHz, CDCl3) delta 0.82 (3H, d, J = 6.8 Hz), 1.08 (3H, d, J = 6.8 Hz), 1.39 (3H, d, J = 6.8 Hz), 1.88-1.97 (1H, m), 3.96 (3H, s), 4.77 (2H, brs), 4.84-4.94 (1H, m), 6.42 (1H, d, J = 2.4 Hz), 7.31 (1H, s), 7.39 (1H, d, J = 2.4 Hz), 10.44 (1H, brs). MS (ESI+) : [M+H]+301.2

Reference： [1]Patent: EP2818473,2014,A1 .Location in patent: Paragraph 0609; 0617

21
[ 844501-71-9 ]
[ 74-88-4 ]
[ 1020174-04-2 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of <strong>[844501-71-9]3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong> (0.5 g, 2.58 mmol, 1 eq) in DMF (5 mL) was added t-buOK (1 M, 5.15 mL, 2 eq). The mixture was stirred at 15 C for 10 min. Then MeI (1.10 g, 7.73 mmol, 481.25 uL, 3 eq) was added. The resulting mixture was stirred at 15 C for another 3 h. The reaction mixture was poured into H2O (10 mL), and extracted with EtOAc (10 mLx3). The combined organic layers were washed with brine (10 mLx2), dried over Na2SO4, filtered and concentrated under reduced pressure to afford the title compound (0.3 g, crude) as yellow oil, which was used into the next step without further purification.

Reference： [1]Patent: WO2018/13867,2018,A1 .Location in patent: Paragraph 684

22
[ 1020174-04-2 ]
[ 130284-52-5 ]
5-chloro-6-(1-methyl-1H-pyrazol-3-yl)pyridin-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; water; at 100.0℃;Inert atmosphere;	Pd2(dba)3 (176.56 mg, 0.19 mmol) and Xphos (183.83 mg, 0.39 mmol) were added to a solution of <strong>[130284-52-5]6-bromo-5-chloropyridin-3-amine</strong> (800 mg, 3.86 mmol), 1 -methyl-3-(4,4,5,5-tetramethyl-i ,3,2-dioxaborolan-2-yl)-1H-pyrazole (1203.52 mg, 5.78 mmol) and K3P04 (2.456 g,11.57 mmol) in dioxane/H20 (6/1, 20 mE) under an N2 atmosphere. The mixture was stirred at 1000 C. overnight. The reaction solution was filtered and the filtrate was concentrated to give a crude product. The crude product was purified by column chromatography over silica gel (petroleum ether/ethyl acetate from 100/0 to 0/100). The desired fractions were collected and the solvent was concentrated under reduced pressure to afford 1 57a (530 mg, 5 9.0% yield) as a yellow solid. ECMS (ESI) mlz M+i: 209.1.

Reference： [1]Patent: US2018/170909,2018,A1 .Location in patent: Paragraph 0887; 0888; 1702; 1703

23
[ 675109-26-9 ]
[ 1020174-04-2 ]
C₁₂H₁₁N₃O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In 1,4-dioxane; water; at 100℃; for 1h;	A mixture of <strong>[675109-26-9]6-bromoisoindolin-1-one</strong> (287 mg, 1.35 mmol), 1-methyl-5-(tributylstannyl)-1H-imidazole (500 mg, 1.35 mmol), Pd(dppf)Cl2 (33 mg, 0.041 mmol) and Cs2CO3 (1.32 g, 4.05 mmol) in dioxane (50 mL) and water (8 mL) was heated to 100 C. overnight. After cooling, the mixture was concentrated under vacuum and purified by column chromatography on silica gel ((1%-3% MeOH in DCM) to afford 9A (220 mg, 76% yield) as a brown solid: 1H NMR (400 MHz, DMSO-d6) delta 8.66 (s, 1H), 7.76-7.15 (m, 4H), 7.15 (s, 1H), 4.43 (s, 2H), 3.72 (s, 3H); ESI m/z 214.1 [M+1]+.

Reference： [1]Patent: US2018/291002,2018,A1 .Location in patent: Paragraph 0423; 0424

24
[ 1020174-04-2 ]
[ 33332-28-4 ]
6-(1-methyl-1H-pyrazol-3-yl)pyrazin-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
28%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 100℃; for 16h;	To a stirred solution of 6-chloropyrazin-2-amine (1 g, 7.72 mmol, 1.0 eq.) and 1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (1.76 g, 8.49 mmol, 1.1 eq.) in dioxane (40 mL) was added Na2CO3 (1.63 g, 15.4 mmol, 2.0 eq.) and 8 mL of water. The reaction mixture was purged with N2 for about 5 min and Pd(dppf)Cl2.DCM complex (0.315 g, 5 mol percent) was added. Reaction mixture was re-purged with N2 and heated at 100° C. for 16 h. Following this, reaction was allowed to cool to RT and extracted using ethyl acetate (3*150 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated under vacuum to obtain the solid residue which was purified by normal phase column chromatography to afford the desired product as brown solid (0.380 g, 28percent).

Reference： [1]Patent: US2019/23666,2019,A1 .Location in patent: Paragraph 0601; 0602; 0603

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P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 1020174-04-2 ]

Quality Control of [ 1020174-04-2 ]

Related Doc. of [ 1020174-04-2 ]

Product Details of [ 1020174-04-2 ]

Safety of [ 1020174-04-2 ]

Application In Synthesis of [ 1020174-04-2 ]

[ 1020174-04-2 ] Synthesis Path-Upstream 1~6

[ 1020174-04-2 ] Synthesis Path-Downstream 1~24

Related Functional Groups of [ 1020174-04-2 ]

Organoboron

Related Parent Nucleus of [ 1020174-04-2 ]

Pyrazoles

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 1020174-04-2 ]

Related Parent Nucleus of
[ 1020174-04-2 ]