[ CAS No. 100960-07-4 ] {[proInfo.proName]}

Name: 100960-07-4|5-Amino-7-azaindole|97%
Brand: Ambeed
SKU: A299680
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Quality Control of [ 100960-07-4 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 100960-07-4 ]

Product Details of [ 100960-07-4 ]

CAS No. :	100960-07-4	MDL No. :	MFCD06659683
Formula :	C₇H₇N₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PLWBENCHEUFMTN-UHFFFAOYSA-N
M.W :	133.15	Pubchem ID :	11715187
Synonyms :

Calculated chemistry of [ 100960-07-4 ]

Physicochemical Properties

Num. heavy atoms :	10
Num. arom. heavy atoms :	9
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	2.0
Molar Refractivity :	40.5
TPSA :	54.7 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.66 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.9
Log Po/w (XLOGP3) :	0.63
Log Po/w (WLOGP) :	1.15
Log Po/w (MLOGP) :	0.37
Log Po/w (SILICOS-IT) :	1.36
Consensus Log Po/w :	0.88

Druglikeness

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

Water Solubility

Log S (ESOL) :	-1.73
Solubility :	2.49 mg/ml ; 0.0187 mol/l
Class :	Very soluble
Log S (Ali) :	-1.35
Solubility :	5.9 mg/ml ; 0.0443 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-2.52
Solubility :	0.404 mg/ml ; 0.00303 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.44

Safety of [ 100960-07-4 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H319	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 100960-07-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 100960-07-4 ]
Downstream synthetic route of [ 100960-07-4 ]

[ 100960-07-4 ] Synthesis Path-Upstream 1~9

1
[ 101083-92-5 ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With palladium 10% on activated carbon; hydrogen In methanol at 20℃; Inert atmosphere	To a stirred solution of 5nitro7azaindoie (500 rng, 3.07 rnmol) in methanol (125 rnL) under nitrogen atmosphere was added 10percent Pd/C (326 mg, 0.306 rnmol). The reaction was placed under an atmosphere of hydrogen gas and stirred at 20 °C overnight. The suspension was filtered through a pad of Celite® 545, the resulting filter cake was washed with MeOH, and the combined organicphases concentrated in vaeuo to afford the title compound (408 mg, 100percent). MS (ES1): mass calcd. for C7HN3 133.1, rn/z found 133.9 [M+H]t. ‘H NMR (300 MHz, DMSO-d6) ö 11.04 (s, 1H), 7.70 (d, J= 2.4 Hz, iH, 7.27 —7.18 (m, 1ff), 7.08 (d, J= 2.3 Hz, IH), 6.22 —6.06 (m, 1H), 4.62 (s, 2H).
95%	With hydrogen In ethyl acetate for 4 h;	To a solution of 5-nitro-1H-pyrrolo[2,3-b]pyridine (0.4 g, 2.45 mmol) in ethyl acetate (100 mL) 5percent Pd-C (0.3 g) was added and the mixture subdued to hydrogenation (30 psi) in a Parr apparatus. After 4 hours the catalyst was filtered off through celite, the cake was washed with ethyl acetate and then with a mixture of dichloromethane/methanol 4:1. 1H-pyrrolo[2,3-b]pyridin-5-amine (5-aminoazaindole) was obtained in 95percent yield (0.31 g, 2.33 mmol). ¹H-NMR (DMSOd₆), δ ppm: 4.62 (s, 2 H) 6.17 (dd, J=3.29, 1.95 Hz, 1 H) 7.10 (dd, J=2.50, 0.55 Hz, 1 H) 7.24 (t, J=2.87 Hz, 1 H) 7.72 (d, J=2.56 Hz, 1 H) 11.04 (s, 1 H).
90%	With hydrogen In tetrahydrofuran; ethanol for 2 h;	Example 12 [Show Image]; (E)-3-(5-Phenylacetylamino-1H-pyrrolo[2,3-b]pyridin-3-yl)-acrylamide; Step 1; 4 gr. (25 mmole) of 5-nitroazaindole (registry number 101083-92-5) were dissolved in 500 ml of ethanol and 150 ml of tetrahydrofuran and hydrogenated with a Parr apparatus after addition of 2 gr of Pd/C 10percent in 2 hrs. After filtration through a plug of celite and recrystallization from toluene/dicloromethane 3 gr of pure 5-aminoazaindole (1) were obtained (90percent yield). 1H NMR (400 MHz, DMSO-D6) δ ppm 4.62 (s, 2 H) 6.17(dd, J=3.29,1.95 Hz, 1 H) 7.10 (dd, J=2.50,0.55 Hz, 1 H) 7.24 (t, J=2.87 Hz, 1 H) 7.72 (d, J=2.56 Hz, 1 H) 11.04 (s, 1 H )

Reference： [1] Patent: WO2016/176460, 2016, A1, . Location in patent: Page/Page column 98; 99
[2] Patent: US2007/112020, 2007, A1, . Location in patent: Page/Page column 36
[3] Patent: EP2070928, 2009, A1, . Location in patent: Page/Page column 92
[4] Synthesis, 2005, # 15, p. 2503 - 2506
[5] Patent: WO2008/28617, 2008, A1, . Location in patent: Page/Page column 41; 27
[6] Patent: WO2016/33100, 2016, A1, . Location in patent: Page/Page column 145; 146

2
[ 1036028-06-4 ]
[ 100960-07-4 ]

Reference： [1] Patent: WO2008/144253, 2008, A1, . Location in patent: Page/Page column 63-64

3
[ 183208-35-7 ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
63%	With ammonia; copper(II) sulfate In waterin a sealed tube; Heating / reflux	[0250] 5-bromo-lH-pyrrolo[2,3-b]ρyridine (6.Og, 30.45mmol) in ammonium hydroxide (12OmL) was treated with copper sulphate pentahydrate (1.50g, 6.09mmol, 0.2 eq) and heated in a sealed tube overnight. The reaction was diluted with EtOAc and the insoluble black solid was filtered off. The filtrate was extracted (EtO Ac/Water) and the organic layer washed with saturated aqueous ammonium chloride, followed by water and brine. The organics were dried over magnesium sulphate, filtered and evaporated to dryness to give the product as a pale brown solid (2.57g, 63percent)

Reference： [1] Patent: WO2008/79346, 2008, A1, . Location in patent: Page/Page column 148

4
[ 25391-56-4 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

5
[ 869884-26-4 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

6
[ 271-63-6 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

7
[ 10592-27-5 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

8
[ 4214-76-0 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

9
[ 118600-53-6 ]
[ 100960-07-4 ]

Reference： [1] Synthesis, 2005, # 15, p. 2503 - 2506

[ 100960-07-4 ] Synthesis Path-Downstream 1~82

2
[ 101083-92-5 ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃;Inert atmosphere;	To a stirred solution of 5nitro7azaindoie (500 rng, 3.07 rnmol) in methanol (125 rnL) under nitrogen atmosphere was added 10% Pd/C (326 mg, 0.306 rnmol). The reaction was placed under an atmosphere of hydrogen gas and stirred at 20 C overnight. The suspension was filtered through a pad of Celite 545, the resulting filter cake was washed with MeOH, and the combined organicphases concentrated in vaeuo to afford the title compound (408 mg, 100%). MS (ES1): mass calcd. for C7HN3 133.1, rn/z found 133.9 [M+H]t. ?H NMR (300 MHz, DMSO-d6) oe 11.04 (s, 1H), 7.70 (d, J= 2.4 Hz, iH, 7.27 -7.18 (m, 1ff), 7.08 (d, J= 2.3 Hz, IH), 6.22 -6.06 (m, 1H), 4.62 (s, 2H).
95%	With hydrogen;5% palladium over charcoal; In ethyl acetate; for 4h;	To a solution of 5-nitro-1H-pyrrolo[2,3-b]pyridine (0.4 g, 2.45 mmol) in ethyl acetate (100 mL) 5% Pd-C (0.3 g) was added and the mixture subdued to hydrogenation (30 psi) in a Parr apparatus. After 4 hours the catalyst was filtered off through celite, the cake was washed with ethyl acetate and then with a mixture of dichloromethane/methanol 4:1. 1H-pyrrolo[2,3-b]pyridin-5-amine (5-aminoazaindole) was obtained in 95% yield (0.31 g, 2.33 mmol). 1H-NMR (DMSOd6), delta ppm: 4.62 (s, 2 H) 6.17 (dd, J=3.29, 1.95 Hz, 1 H) 7.10 (dd, J=2.50, 0.55 Hz, 1 H) 7.24 (t, J=2.87 Hz, 1 H) 7.72 (d, J=2.56 Hz, 1 H) 11.04 (s, 1 H).
90%	With hydrogen;palladium 10% on activated carbon; In tetrahydrofuran; ethanol; for 2h;	Example 12 [Show Image]; (E)-3-(5-Phenylacetylamino-1H-pyrrolo[2,3-b]pyridin-3-yl)-acrylamide; Step 1; 4 gr. (25 mmole) of 5-nitroazaindole (registry number 101083-92-5) were dissolved in 500 ml of ethanol and 150 ml of tetrahydrofuran and hydrogenated with a Parr apparatus after addition of 2 gr of Pd/C 10% in 2 hrs. After filtration through a plug of celite and recrystallization from toluene/dicloromethane 3 gr of pure 5-aminoazaindole (1) were obtained (90% yield). 1H NMR (400 MHz, DMSO-D6) delta ppm 4.62 (s, 2 H) 6.17(dd, J=3.29,1.95 Hz, 1 H) 7.10 (dd, J=2.50,0.55 Hz, 1 H) 7.24 (t, J=2.87 Hz, 1 H) 7.72 (d, J=2.56 Hz, 1 H) 11.04 (s, 1 H )

	With hydrogen;platinum on activated charcoal; In tetrahydrofuran; at 20℃; under 760.051 Torr; for 3h;	2.675 g 5-Nitro-lH-pyrrolo[2,3-b]pyridine in 200 ml THF were hydrogenated over 1.0 g Platinum on carbon at atmospheric pressure for 3 hrs at RT (with thin layer chromatography (TLC) control). The catalyst was removed by filtration, the filtrate was evaporated and the residue purified by chromatography on silica in ethyl acetate /heptane mixtures. Yield 1.84 g
	With palladium on activated charcoal; hydrogen; for 18h;	Example 97: Preparation of l -pyrrolo[2,3-b]pyridin-5-amine5-Nitro- lH-pyrrolo[2,3-b]pyridine (1.0 g, 6.13 mmol, 1.0 equiv) and palladium on carbon (75 mg) were mixed in EtOAc (20 mL). A balloon of hydrogen gas was applied for 18 h, then the mixture was filtered through Celite with DCM and concentrated in vacuo. The resultant brown solid (800 mg) was used without further purification. MS calcd for [C7H7N3+H]+: 134.07, found 134.16.

Reference： [1]Patent: WO2016/176460,2016,A1 .Location in patent: Page/Page column 98; 99
[2]Patent: US2007/112020,2007,A1 .Location in patent: Page/Page column 36
[3]Patent: EP2070928,2009,A1 .Location in patent: Page/Page column 92
[4]Synthesis,2005,p. 2503 - 2506
[5]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 41; 27
[6]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 145; 146

3
[ 100960-07-4 ]
[ 25784-91-2 ]
[ 1012342-14-1 ]

Yield	Reaction Conditions	Operation in experiment
		1.87 g lH-Pyrrolo [2,3-b] pyridin-5-ylamine in 60 ml dry pyridine were treated dropwise at RT with a solution of 6.79 g 2-chloro-5-nitrobenzoyl chloride in 10 ml dichloromethane. Stirring was continued over night. The mixture was evaporated and the residue was treated with 25 ml methanol and 10 ml cone, ammonia for2 hrs at RT. The solvents are again evaporated and the residue is dispersed in water. The crude product is isolated by filtration and washed thoroughly with water and diethylether. Yield 3.85 g

Reference： [1]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 41

4
[ 100960-07-4 ]
[ 30459-70-2 ]
[ 1012342-27-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In acetonitrile; at 20℃; for 16h;	2-Methyl-5-nitro-N-(lH-pyrrolo[2,3-b]pyridin-5-yl)-benzamide To a solution of 2-methyl-4-nitrobenzoic acid (2 g, 11 mmol) in benzene (40 ml) was added thionyl chloride (2 ml) and refluxed for 3 h. The reaction mixture was concentrated, diluted with dry acetonitrile (20 ml). To this solution was added dry K2CO3 (2 g, 14 mmol) followed by a solution of lH-Pyrrolo[2,3-b]pyridin-5- ylamine (example c), 1.4 g, l lmmol) in acetonitrile (20 ml) and the reaction mixture and stirred for 16 h at RT. Solvent was removed under reduced pressure, diluted with water stirred for 15 min and filtered. The solid residue was washed with EtOAc to get 2.4 g of crude title product. LC-MS: (m/z 297)

Reference： [1]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 56

5
[ 100960-07-4 ]
[ 120890-66-6 ]
[ 1012342-29-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In acetonitrile; at 20℃; for 16h;	To a solution of 2-chloro-4-fluoro-5-nitrobenzoic acid from example d-2 (2 g, 9.1 mmol) in benzene (40 ml) was added thionyl chloride (2 ml) and refluxed for 3 h. The reaction mixture was concentrated, diluted with dry acetonitrile (20 ml). To this solution dry K2CO3 (2 g, 14 mmol) was added, followed by a solution of IH- Pyrrolo[2,3-b]pyridin-5-ylamine (example c),1.2 g, 9.1 mmol) in acetonitrile (20 ml) and the reaction mixture was stirred for 16 h at RT. Filtered the reaction mixture through cintered faunal. The residue was washed with dry acetonitrile several times. Solvent was removed under reduced pressure, 2.8g of the crude title product. LC-MS: (m/z 335)

Reference： [1]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 58

6
[ 100960-07-4 ]
[ 1012342-31-2 ]
[ 1012342-33-4 ]

Yield	Reaction Conditions	Operation in experiment
	With dmap; benzotriazol-1-ol; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; In tetrahydrofuran; at 20℃;	To a solution of lH-pyrrolo[2,3-b]pyridin-5-ylamine (example c), 0.5 mmol) and 4-methyl-isophthalic acid 1-tert-butyl ester from example 1-1 (0.5 mmol) in THF (5 ml) were added TBTU (0.5 mmol), HOBT (0.5 mmol) and Hunig's base(0.6 mmol) and stirred at RT for overnight. Solvent was concentrated, residue was diluted with EtOAc ( ) .washed with l(N) NaOH. Organics was concentrated to get 2.8g of the crude title product. LC-MS: (m/z 352)

Reference： [1]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 61

7
[ 25391-56-4 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

8
[ 869884-26-4 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

9
[ 271-63-6 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

10
[ 10592-27-5 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

11
[ 4214-76-0 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

12
[ 118600-53-6 ]
[ 100960-07-4 ]

Reference： [1]Synthesis,2005,p. 2503 - 2506

13
[ 100960-07-4 ]
[ 64-19-7 ]
[ 937012-21-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	With benzotriazol-1-ol; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 18.5h;	Into a solution of 5-aminoazaindole (0.6 g, 4.5 mmol) in dry DMF (11 mL) N-[(1H-1,2,3-benzotriazol-1-yloxy)(dimethylamino)methylene]-N-methylmethanam inium tetrafluoroborate (TBTU, 1.45 g, 9 mmol), 1-hydroxybenzotriazole (HOBt, 0.69 g, 9 mmol) and glacial AcOH (260 micro), diisopropylethylamine (DIPEA, 3.12 mL, 18 mmol) was slowly dropped in ca. 30' under stirring. The reaction mixture was stirred at room temperature for 18 h, concentrated and the residue was purified by flash chromatography eluting with dichloromethane/MeOH 10:1. The desired 1H-pyrrolo[2,3-b]pyridin-5-ylacetamide (title compound) was obtained in 95% yield (0.78 g, 4.2 mmol). 1H-NMR (DMSOd6), delta ppm: 2.07 (s, 3 H) 6.41 (m, 1 H) 7.43 (t, J=2.93 Hz, 1 H) 8.22 (d, J=2.07 Hz, 1 H) 8.26 (d, J=2.32 Hz, 1 H) 9.92 (s, 1 H) 11.51 (s, 1 H).

Reference： [1]Journal of Medicinal Chemistry,2009,vol. 52,p. 4380 - 4390
[2]Patent: US2007/112020,2007,A1 .Location in patent: Page/Page column 36

14
[ 100960-07-4 ]
[ 1885-14-9 ]
[ 1020325-69-2 ]

Yield	Reaction Conditions	Operation in experiment
23%	With pyridine; In tetrahydrofuran; acetonitrile;	Example 13; Synthesis of N-1H-pyrrolo[2,3-b]pyridin-6-yl-4-(3-[5-(trifluoromethyl)pyridin-2-yl]oxy}benzylidene) piperidine-1-carboxamide; Step 1; Phenyl 1H-pyrrolo[2,3-b]pyridin-5-ylcarbamate; To a solution of <strong>[100960-07-4]1H-pyrrolo[2,3-b]pyridin-5-ylamine</strong> (0.50 g, 3.7 mmol, see Synthesis, 2005, No. 15, 2503-2506) in THF (4 mL) and CH3CN (6 mL) was added pyridine (0.36 mL, 4.4 mmol) followed by phenyl chloroformate (0.49 mL, 3.8 mmol) slowly. The reaction was stirred overnight. The mixture was partitioned between water and EtOAc. The aqueous layer was extracted again with EtOAc. The combined organic layer was dried over sodium sulfate, filtered and concentrated. Purification by chromatography (0-100% EtOAc/hexane) provided the desired product as a white solid (0.213 g, 23%). MS M+1: 254.15.
23%	With pyridine; In tetrahydrofuran; acetonitrile;	To a solution of 1 H-pyrrolo[2,3-b]pyridin-5-ylamine (0.50 g, 3.7 mmol; Synthesis, 2005, 2503-2506; CASNo. 100960-07-4) in THF (4 mL) and CH3CN (6 mL) was added pyridine (0.36 mL, 4.4 mmol) followed by phenyl chloroformate (0.49 mL, 3.8 mmol) slowly. The reaction was stirred overnight. The mixture was partitioned between water and EtOAc. The aqueous layer was extracted again with EtOAc. The <n="32"/>combined organic layer was dried over sodium sulfate, filtered and concentrated. Purification by chromatography (0-100% EtOAc/hexane) provided the desired product as a white solid (0.213 g, 23%). m/z 254.15 (MH+).
23%	With pyridine; In tetrahydrofuran; acetonitrile;	To a solution of 1 H-pyrrolo[2,3-b]pyridin-5-ylamine (0.50 g, 3.7 mmol; Synthesis, 2005, 2503-2506; CASNo. 100960-07-4) in THF (4 mL) and CH3CN (6 mL) was added pyridine (0.36 mL, 4.4 mmol) followed by phenyl chloroformate (0.49 mL, 3.8 mmol) slowly. The reaction was stirred overnight. The mixture was partitioned between water and EtOAc. The aqueous layer was extracted again with EtOAc. The combined organic layer was dried over sodium sulfate, filtered and concentrated. Purification by chromatography (0-100% EtOAc/hexane) provided the desired product as a white solid (0.213 g, 23%). m/z 254.15 (MH+).

Reference： [1]Patent: US2008/261941,2008,A1 .Location in patent: Page/Page column 21
[2]Patent: WO2009/127949,2009,A1 .Location in patent: Page/Page column 30; 31
[3]Patent: WO2009/127948,2009,A1 .Location in patent: Page/Page column 31
[4]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 7357 - 7362

15
[ 100960-07-4 ]
[ 501-53-1 ]
[ 1036028-06-4 ]

Yield	Reaction Conditions	Operation in experiment
77%		[0251] lH-pyrrolo[2,3-b]pyridin-5-amine (9.45g, 71.05mmol) was dissolved in THF(15OmL) and stirred at 0 C under an atmosphere of nitrogen. Benzyl chloro formate (20.3mL, <n="150"/>142.10mmol, 2.0Eq) was added dropwise over a period of 15 minutes and the mixture allowed to stir at room temperature for 30 minutes. The mixture was treated with 4M NaOH (aq) (53.3mL, 213. lmmol, 3.0Eq) over a period of 15 minutes and the resultant brown solution left to stir for 16 hours. The reaction mixture was taken to pH 4 (125mL of 10% aq. citric acid) and the 2 layers were separated. The aqueous layer was back extracted with EtOAc and the combined organics were dried over magnesium sulphate, filtered and dried under vacuum. The crude product was purified by column chromatography (50% EtOAc/ Petroleum Ether) to give 14.59g (77%) of pale yellow solid.
75%	With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 20℃; for 0.5h;	A mixture of <strong>[100960-07-4]5-amino-7-azaindole</strong> (5 g, 37.6 mmol) and DIPEA (13 mL, 75 mmol) in dichloromethane (300 mL) was stirred at room temperature. Benzyl chloroformate (5.8 mL, 38.3mmol) was added dropwise with stir. The reaction was stirred at RT for 30 mm. The reaction mixture was concentrated and then dissolved in EtOAc and washed with diluted (0.2 to 0.3 N) HCl aqueous solution and brine. The organic solution was dried over Na2SO4 and concentrated. The residue was dissolved in small amount of THF and purified by flash chromatography (Silica gel 60, 230-400 mesh, 0-80 % EtOAc in hexanes) to give (1H-pyrrolo[2,3-b]pyridin-5-yl)-carbamic acid benzyl ester (7.55 g, 75 % yield) as a light brown solid. LCMS calcd for C15H13N3O2 (m/e) 267, obsd 268 (M+H).

Reference： [1]Patent: WO2008/79346,2008,A1 .Location in patent: Page/Page column 148; 149
[2]Patent: WO2014/161799,2014,A1 .Location in patent: Page/Page column 48

16
[ 183208-35-7 ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
63%	With ammonia; copper(II) sulfate; In water;in a sealed tube; Heating / reflux;	[0250] 5-bromo-lH-pyrrolo[2,3-b]rhoyridine (6.Og, 30.45mmol) in ammonium hydroxide (12OmL) was treated with copper sulphate pentahydrate (1.50g, 6.09mmol, 0.2 eq) and heated in a sealed tube overnight. The reaction was diluted with EtOAc and the insoluble black solid was filtered off. The filtrate was extracted (EtO Ac/Water) and the organic layer washed with saturated aqueous ammonium chloride, followed by water and brine. The organics were dried over magnesium sulphate, filtered and evaporated to dryness to give the product as a pale brown solid (2.57g, 63%)

Reference： [1]Patent: WO2008/79346,2008,A1 .Location in patent: Page/Page column 148

17
[ 651744-49-9 ]
[ 100960-07-4 ]
[ 1036963-06-0 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 2985 - 2989

18
[ 100960-07-4 ]
[ 75177-59-2 ]
[ 1086423-68-8 ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; HATU; In N,N-dimethyl-formamide; at 20℃; for 2h;	A mixture of lH-pyrrolo[2,3-b]pyridin-5-amine (28 mg, 0.2 mmol), 2,6-dichloro-3,5- dimethoxybenzoic acid (50 mg, 0.2 mmol), HATU (76 mg, 0.2 mmol), DIEA (77 mg, 0.6 mmol) in 1 ml DMF is stirred for 2 hours at room temperature. The reaction mixture is neutralized with acetic acid and purified by reverse phase HPLC to give the title compound as light gray solid. 1H NMR 600 MHz (DMSO-J6) delta 11.61 (s, IH), 10.61 (s, IH), 8.30 (d, 1 H, J = 2.0 Hz), 8.27 (d, 1 H, J = 2.0 Hz), 7.43 (U H, J = 2.8 Hz), 6.95(5, IH), 6.41 (m, IH), 3.90 (s, 6H); MS m/z 366.1 (M + 1).

Reference： [1]Patent: WO2008/144253,2008,A1 .Location in patent: Page/Page column 63-64

19
[ 1036028-06-4 ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen;palladium dihydroxide; In ethanol; at 20℃; for 6h;	To a solution of benzyl lH-pyrrolo[2,3-b]pyridin-5-ylcarbamate (1.38 g, 5.2 mmol) in 80 ml ethanol is added 150 mg Pd(OH)2. The mixture is stirred at room temperature for 6 hours with a hydrogen balloon attached. The reaction mixture is flushed with nitrogen and <n="65"/>P A T E N TGNF Docket No.: P1267PC10 filtered through a celite pad to remove the Pd(OH)2. The filtrate is evaporated and dried to give the title compound as light brown oil. MS m/z 134.1 (M + 1).

Reference： [1]Patent: WO2008/144253,2008,A1 .Location in patent: Page/Page column 63-64

20
[ 103-82-2 ]
[ 100960-07-4 ]
[ 1160985-06-7 ]

Yield	Reaction Conditions	Operation in experiment
83%	With benzotriazol-1-ol; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃;	Step 2; 600 mg (4.56 mmole ) of 5-aminoazaindole were dissolved in 12 ml of anhydrous DMF and, after addition of 675 mg (4.96 mmole) of phenylacetic acid, 1.6 gr (4.96 mmole) of TBTU, 758 mg (4.96 mmole) of HOBT and 3.4 ml (19.4 mmole) of DIPEA, the reaction was stirred overnight at r.t. Evaporation of the solvent and estraction with ethyl acetate gave, after alkaline washing, 950 mg of 2-phenyl-N- (1H-pyrrolo[2,3-b]pyridin-5-yl)-acetamide (2) (83% yield). 1H NMR (400 MHz, DMSO-D6) delta ppm 3.67 (s, 2 H) 6.40(dd, J=3.41,1.83 Hz, 1 H) 7.26-7.36 (m, 5 H) 7.44 (t, J=3.05 Hz, 1 H) 8.20 (d, J=2.32 Hz, 1 H) 8.30 (d, J=5.28 Hz, 1 H) 10.16 (s, 1 H) 11.52 (bs, 1 H)

Reference： [1]Patent: EP2070928,2009,A1 .Location in patent: Page/Page column 92-93

21
[ 100960-07-4 ]
[ 1012342-20-9 ]
[ 1012342-21-0 ]

Yield	Reaction Conditions	Operation in experiment
		4.16 g 4-Chloro-isophthalic acid 1-tert-butyl ester in 10 ml dry DMF were stirred with 2.63 g carbonyldiimidazole for 1 hr at room temperature. 1.80 g IH- Pyrrolo[2,3-b]pyridin-5-ylamine and 10 mg 4-dimethylaminopyridine were added and the mixture was heated to 600C. After 4 hrs, the solvent was removed under vacuum and the residue was dissolved in a mixture of 5 ml methanol and 5 ml concentrated ammonia. After stirring for 20 min at room temperature, the mixture was again evaporated and the residue purified by chromatography on silica in ethyl acetate / heptane mixtures. Yield 3.00 g of the title product.

Reference： [1]Patent: WO2008/28617,2008,A1 .Location in patent: Page/Page column 43

22
[ 100960-07-4 ]
[ 921040-10-0 ]
[ 1187421-27-7 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of 150 mg (0.43 mmol) of ethyl 5-trifluoromethyl-1-[(pyrid-4-yl)methyl)]-1H-indole-2-carboxylate, obtained according to the protocol described in the preceding step, and 69 mg (0.52 mmol) of pyrrolo[2,3-b]pyrid-5-ylamine in 1.5 mL of dry toluene, maintained under an inert atmosphere, is added dropwise, at 0 C., 0.32 mL (0.645 mmol) of a solution of trimethylaluminium (2M/toluene). The reaction mixture is stirred at 110 C. for 15 hours and then concentrated under reduced pressure. The crude reaction product is then diluted with 50 mL of normal HCl solution and 100 mL of ethyl acetate. The organic phase is separated out, washed with 50 mL of saturated sodium chloride solution and then dried over sodium sulfate and concentrated under reduced pressure. The resulting product is purified by chromatography on a column of silica. 147 mg of the expected product are thus isolated.1H NMR (DMSO D6), delta (ppm): 11.62 (s, 1H); 10.62 (s, 1H); 8.47 (d, 2H); 8.42 (s, 1H), 8.29-8.24 (m, 2H); 7.76 (d, 1H); 7.66 (s, 1H); 7.58 (dd, 1H); 7.46 (t, 1H); 7.03 (d, 2H); 6.45-6.43 (m, 1H); 6.00 (s, 2H).LC-MS: 436 [M+H]+ m.p.=216-217 C.

Reference： [1]Patent: US2011/9364,2011,A1 .Location in patent: Page/Page column 12-13

23
[ 100960-07-4 ]
[ 1268520-96-2 ]
[ 1279724-66-1 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 1270 - 1274

24
[ 100960-07-4 ]
C₁₁H₁₁N₃O₂ [ No CAS ]
[ 1279724-67-2 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 1270 - 1274

25
[ 100960-07-4 ]
[ 1268520-84-8 ]
[ 1279724-68-3 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 1270 - 1274

26
[ 100960-07-4 ]
[ 1103234-56-5 ]
[ 1186499-89-7 ]

Reference： [1]ACS Medicinal Chemistry Letters,2011,vol. 2,p. 342 - 347

27
[ 10400-19-8 ]
[ 100960-07-4 ]
[ 1312942-06-5 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In tetrahydrofuran; at 20℃; for 16h;	In a reaction vial, 1 H-Pyrrolo[2,3-b]pyridin-5-ylamine (35, 0.1 g, 0.8 mmol) is dissolved in 7 mL of tetrahydrofuran and triethylamine (0.10 mL, 0.75 mmol) and nicotinoyi chloride (36, 0.16 g, 1. 1 mmol) are added. The reaction is stirred at room temperature for 16 hours, then diluted with water and extracted 3x with ethyl acetate. The organic layers are combined and washed with brine, then dried over sodium sulfate, filtered and the filtrate concentrated under vacuum to provide the desired compound.

Reference： [1]Patent: WO2011/79133,2011,A2 .Location in patent: Page/Page column 202; 203

28
[ 10400-19-8 ]
[ 100960-07-4 ]
[ 1312940-90-1 ]

Reference： [1]Patent: WO2011/79133,2011,A2

29
[ 100960-07-4 ]
[ 1227934-77-1 ]
[ 1227932-45-7 ]

Yield	Reaction Conditions	Operation in experiment
		Example 54 N-[1H-pyrrolo[2,3-b]pyridin-5-yl]-2-(3-methyl-1-piperidinyl)-4-(trifluoromethyl)-5-oxazolecarboxamide (54) Compound 54 was prepared by the general procedure for compound I, by using compound A-10 and <strong>[100960-07-4]5-amino-7-azaindole</strong> as starting materials. 1H NMR (500 MHz, DMSO-d6) 11.67 (s, 1H), 10.21 (s, 1H), 8.37 (s, 1H), 8.23 (s, 1H), 7.50 (s, 1H), 6.46 (m, 1H), 4.13 (m, 2H), 3.07 (m, 1H), 2.75 (t, 1H, J=11.7 Hz), 1.77 (m, 2H), 1.67 (m, 1H), 1.54 (m, 1H), 1.15 (m, 1H), 0.94 (d, 3H, J=6.3 Hz). MS (M+1): 394.

Reference： [1]Patent: US2011/224137,2011,A1

30
[ 100960-07-4 ]
[ 4748-78-1 ]
N-(4-ethylbenzyl)-1H-pyrrolo[2,3-b]pyridin-5-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%		Synthesis of N- (4-ethylbenzyl) -1H-pyrrolo[2 ,3-b]pyridin-5- amine (compound 66-2)[0000234] To a stirred solution of 1H-pyrrolo[2,3-b]pyridin- 5-amine (0.5 g, 3.8 mmol, 1 equiv) in methanol (20 ml) was added 4-ethyl benzaldehyde (566 IlL, 4.1 mmol, 1.1 equiv) Acetic acid (5 drops) was added and the reaction was stirred for 2 hours during which time a white solid formed. Dichloromethane (30 mL) was added to dissolve the entire solid. Sodium borohydride (700 mg) was added portionwise until all intermediate imine was consumed by LC-MS analysis. The reaction was poured into water (50 mL) and the layers were separated. The aqueous phase was extracted with dichloromethane (3 x 10 mL) . The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure. This residue was triturated with methyl tert-butyl ether (2 x 8 mL) to give compound 66-2 as an off- white solid (640 mg, 68% yield)

Reference： [1]Patent: WO2013/123215,2013,A2 .Location in patent: Paragraph 0000234

31
[ 100960-07-4 ]
[ 4748-78-1 ]
[ 1421589-51-6 ]

Reference： [1]Patent: WO2013/123215,2013,A2

32
[ 100960-07-4 ]
[ 24424-99-5 ]
[ 1616388-24-9 ]

Yield	Reaction Conditions	Operation in experiment
22%	With dmap; N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 20℃;	Into a round bottom flask were placed lH-pyrrolo[2,3-b]pyridin-5-amine 121 (1 g, 7.51 mmol), di-tert-butyldicarbonate (6.5 g, 29.78 mmol), 4-dimethylaminopyridine (0.03 g, 0.23 mmol) and N,N-diisopropylethylamine (5 ml, 28.71 mmol) in tetrahydrofuran (20 mL). The reaction was stirred at room temperature overnight, then concentrated. The residue was mixed with water and brine and extracted with ethyl acetate. The organic layers were dried over anhydrous sodium sulfate and evaporated to dryness. The resulting solid was purified by silica gel chromatography to provide compound 122 (0.73 g, 22%) MS ESI [M+H+]+ = 434.3. 1H NMR and mass spectroscopy data were consistent with the desired product.

Reference： [1]Patent: WO2014/100620,2014,A2 .Location in patent: Paragraph 0365

33
[ 100960-07-4 ]
[ 1616387-98-4 ]

Reference： [1]Patent: WO2014/100620,2014,A2

34
[ 100960-07-4 ]
[ 1616385-50-2 ]

Reference： [1]Patent: WO2014/100620,2014,A2
[2]Patent: WO2014/100620,2014,A2

35
[ 100960-07-4 ]
[ 1616386-96-9 ]

Reference： [1]Patent: WO2014/100620,2014,A2

36
[ 100960-07-4 ]
[ 1616385-66-0 ]

Reference： [1]Patent: WO2014/100620,2014,A2

37
[ 100960-07-4 ]
[ 1616388-25-0 ]

Reference： [1]Patent: WO2014/100620,2014,A2

38
[ 100960-07-4 ]
[ 1616388-26-1 ]

Reference： [1]Patent: WO2014/100620,2014,A2

39
[ 100960-07-4 ]
[ 1616388-27-2 ]

Reference： [1]Patent: WO2014/100620,2014,A2

40
[ 100960-07-4 ]
[ 1616388-28-3 ]

Reference： [1]Patent: WO2014/100620,2014,A2

41
[ 100960-07-4 ]
3-(3-aminophenyl)-5-benzyloxycarbonylaminopyrrolo[2,3-b]pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

42
[ 100960-07-4 ]
(3-iodo-1H-pyrrolo[2,3-b]pyridin-5-yl)carbamic acid benzyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

43
[ 100960-07-4 ]
5-benzyloxycarbonylamino-3-iodopyrrolo[2,3-b]pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

44
[ 100960-07-4 ]
3-(2-aminophenyl)-5-benzyloxycarbonylaminopyrrolo[2,3-b]pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

45
[ 100960-07-4 ]
4-(5-amino-1H-pyrrolo[2,3-b]pyridin-3-yl)piperidine-1-carboxylic acid tert-butyl [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

46
[ 100960-07-4 ]
4-[5-(2-chlorobenzyloxycarbonylamino)-1H-pyrrolo[2,3-b]pyridin-3-yl]-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

47
[ 100960-07-4 ]
{3-[3-((E)-4-dimethylaminobut-2-enoylamino)phenyl]-1H-pyrrolo[2,3-b]pyridin-5-yl}carbamic acid benzyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

48
[ 100960-07-4 ]
5-benzyloxycarbonylamino-3-[3-((E)-4-dimethylaminobut-2-enoylamino)phenyl]pyrrolo[2,3-b]pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

49
[ 100960-07-4 ]
{3-[1-(2-oxopropionyl)-1,2,3,6-tetrahydropyridin-4-yl]-1H-pyrrolo[2,3-b]pyridin-5-yl}carbamic acid 2-chlorobenzyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

50
[ 100960-07-4 ]
[3-(1,2,3,6-tetrahydropyridin-4-yl)-1H-pyrrolo[2,3-b]pyridin-5-yl]carbamic acid 2-chlorobenzyl ester [ No CAS ]

Reference： [1]Patent: WO2014/161799,2014,A1

51
[ 100960-07-4 ]
[ 79099-07-3 ]
4-(5-amino-1H-pyrrolo[2,3-b]pyridin-3-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium methylate; In methanol; at 80℃; for 2h;	<strong>[100960-07-4]5-amino-7-azaindole</strong> (2.9 g, 21.8 mmol) was dissolved in methanol (80 mL). 1-BOC-4-piperidone (5.95 g, 29.8 mmol) and sodium methoxide (11.8 g, 12.5 mL, 54.4 mmol) were added. The reaction mixture was heated at 80 C for 2 hr. The reaction was concentrated. The residue was diluted with EtOAc. The organic layer was washed with saturated NaHCO3 and brine, dried and concentrated. The residue was purified by flash chromatography (silica gel, 0-8 % MeOH in DCM) to give 4-(5-amino-1H-pyffolo[2,3-b]pyridin-3-yl)-3,6-dihydro-2H-pyridine-1-carboxylicacid tert-butyl ester (6.13 g, 90 %) as a light yellow solid. LCMS calcd. for C17H22N4O2 (m/e)314, obsd. 315 (M+H)

Reference： [1]Patent: WO2014/161799,2014,A1 .Location in patent: Page/Page column 55

52
[ 398489-26-4 ]
[ 100960-07-4 ]
3-(5-amino-1H-pyrrolo[2,3-b]pyridin-3-yl)-3-hydroxyazetidine-1-carboxylic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%	With potassium hydroxide; In methanol; at 75℃; for 72h;	<strong>[100960-07-4]5-amino-7-azaindole</strong> (1.0 g, 7.51 mmol) was dissolved in methanol (30 mL). 1-BOC-3-azetidinone (1.54 g, 9.01 mmol) and potassium hydroxide (0.52 g, 9.29 mmol) were added. The reaction mixture was heated at 75 C for 3 days. The reaction was concentrated. The residue was diluted with EtOAc. The organic layer was washed with water and brine, dried over Na2SO4and concentrated. The residue was purified by flash chromatography (silica gel, 5-8 % MeOH in DCM) to give 3 -(5-amino-1H-pyrrolo[2, 3-blpyridin-3-yl)-3-hydroxy-azetidine-1-carboxylic acid tert-butyl ester (0.79 g, 35 %) as a light yellow solid. LCMS calcd. for C15H20N403 (m/e) 304, obsd. 305 (M+H)

Reference： [1]Patent: WO2014/161799,2014,A1 .Location in patent: Page/Page column 56

53
[ 100960-07-4 ]
[ 3932-97-6 ]
[ 74-89-5 ]
N⁴-methyl-N²-(1 H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]
N²-methyl-N⁴-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20 mg; 11 mg		Example 182: Preparation of N4-methyl-N2-(lH-pyrrolo[2,3-b]pyridin-5-yl)-5- (trifluoromethyl)pyrimidine-2,4-diamine and N2-methyl-N4-(lH-pyrrolo[2,3-b]pyridin-5- yl)- -(trifluoromethyl)pyrimidine-2,4-diamineN-(4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)-lH-pyrrolo[2,3-b]pyridin-5-amine (0.100 g, 0.319 mmol, contains 30% of the regioisomer) and methanamine (0.1 19 ml, 0.956 mmol) were mixed in DMF (2 mL). The mixture was microwaved at 100 C for 20 minutes and then concentrated. 20 mg of N4-methyl-N2-(lH-pyrrolo[2,3-b]pyridin-5-yl)-5- (trifluoromethyl)pyrimidine-2,4-diamine and 1 1 mg of N2-methyl-N4-(lH-pyrrolo[2,3-b]pyridin- 5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine were recovered after automated reverse phase chromatography (water- eCN eluent). MS calcd for [CuHuFsNe+H]"1": 309.1 1 , found 308.95

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 180; 181

54
[ 100960-07-4 ]
N⁴-(benzo[d][1,3]dioxol-5-yl)-N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Reference： [1]Patent: WO2016/33100,2016,A1

55
[ 100960-07-4 ]
N⁴-(2-methoxyethyl)-N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Reference： [1]Patent: WO2016/33100,2016,A1

56
[ 100960-07-4 ]
N⁴-(oxetan-3-yl)-N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Reference： [1]Patent: WO2016/33100,2016,A1

57
[ 100960-07-4 ]
2-((1H-pyrrolo[2,3-b]pyridin-5-yl)amino)-5-(trifluoromethyl)pyrimidin-4-ol [ No CAS ]

Reference： [1]Patent: WO2016/33100,2016,A1

58
[ 100960-07-4 ]
[ 3932-97-6 ]
[ 62-53-3 ]
N⁴-phenyl-N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]
N⁴-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
19 mg; 15 mg		Example 181: Preparation of N4-phenyl-N2-(lH-pyrrolo[2,3-b]pyridin-5-yl)-5- (trifluoromethyl)pyrimidine-2,4-diamine and N4-(lH-pyrrolo[2,3-b]pyridin-5-yl)-5- (trifluoromethyl)pyrimidine-2,4-diamineN-(4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)-lH-pyrrolo[2,3-b]pyridin-5-amine (0.1 00 g, 0.31 9 mmol, contains 30% of the regioisomer), aniline (0.029 ml, 0.319 mmol) and N-ethyl-N- isopropylpropan-2-amine (0.1 1 1 ml, 0.638 mmol) were mixed in Acetonitrile (2 ml). The mixture was microwaved at 130 C for 20 minutes and then concentrated. In order to degrade the unreacted minor starting material regioisomer, ammonia (455 mL, 7M in MeOH), was added and the mixture was microwaved at 120 C for 20 minutes. 19 mg of N4-phenyl-N2-(l H-pyrrolo[2,3- b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine and 15 mg of N4-(l H-pyrrolo[2,3- b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine were recovered after automated reverse phase chromatography (water-MeCN eluent). MS calcd for [CigH] 3F3N6+H]+: 371 .13, found 371.10. MS calcd for [Ci2H9F3N6+H]+: 295.09, found 294.85.

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 180

59
[ 100960-07-4 ]
2-chloro-N-cyclopropylpyrimidin-4-amine [ No CAS ]
N⁴-cyclopropyl-N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)pyrimidine-2,4-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
18 mg	With acetic acid; at 120℃; for 0.166667h;Microwave irradiation;	Example 204: Preparation of N4-cyclopropyl-N2-(lH-pyrroIo[2,3-b]pyridin-5- yl)pyrimidine-2,4-diamine2-Chloro-N-cyclopropylpyrimidin-4-amine (0.070 g, 0.413 mmol) and lH-pyrrolo[2,3- b]pyridin-5-amine (0.055 g, 0.413 mmol) were mixed in Acetic Acid (1 ml). The mixture was microwaved at 120 C for 10 minutes and then concentrated. 18 mg of product was recovered after automated reverse phase chromatography (water-MeCN eluent). MS calcd for[C14H14N6+H]+: 267.14, found 266.80.

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 189; 190

60
[ 100960-07-4 ]
[ 3932-97-6 ]
[ 4141-08-6 ]
2-((2-((1H-pyrrolo[2,3-b]pyridin-5-yl)amino)-5-(trifluoromethyl)pyrimidin-4-yl)amino)-N-methylbenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34 mg		Example 201: Preparation of 2-((2-((lH-pyrrolo[2,3-b]pyridin-5-yl)amino)-5-(trifluoro methyl) pyrimidin-4-yl)amino)-N-methylbenzamide2,4-Dichloro-5-(trifluoromethyl)pyrimidine (0.085 g, 0.392 mmol), 2-amino-N- methylbenzamide (0.059 g, 0.392 mmol) and N-ethyl-N-isopropylpropan-2-amine (0.068 ml, 0.392 mmol) were mixed in Acetonitrile (1 ml). The mixture was microwaved at 90 C for 10 minutes and then concentrated. lH-pyrrolo[2,3-b]pyridin-5-amine (0.052 g, 0.392 mmol) and acetic acid (0.024 g, 0.392 mmol) were added. The mixture was microwaved at 1 10 C for 1 0 minutes and then concentrated. Added methanol and filtered the solid, then washed with THF. 34 mg of product was isolated. MS calcd for [C2oHi6F3N70+H]+: 428.15, found 428.15.

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 188; 189

61
[ 100960-07-4 ]
[ 3932-97-6 ]
N-(4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)-1H-pyrrolo[2,3-b]pyridin-5-amine [ No CAS ]
N-(2-chloro-5-(trifluoromethyl)pyrimidin-4-yl)-1H-pyrrolo[2,3-b]pyridin-5-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; zinc(II) chloride; In dichloromethane; tert-butyl alcohol; at -10 - 21℃; for 1h;Inert atmosphere;	Example 176: Preparation of N-(4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)-lH- pyrrolo[2,3-b]pyridin-5-amine and N-(2-chloro-5-(trifluoromethyl)pyrimidin-4-yl)-lH- pyrrolo[2,3-b ridin-5-amineTo 2,4-dichloro-5-(trifluoromethyl)pyrimidine (0.4 g, 1 .844 mmol) in Dichloromethane (5 ml) and t-Butanol (5.00 ml) at - 10 C under nitrogen was added zinc(II) chloride (0.502 g, 3.69 mmol). Kept at - 10 to 0 C for 1 h. lH-pyrrolo[2,3-b]pyridin-5-amine (0.245 g, 1 .844 mmol) and triethylamine (0.283 ml, 2.028 mmol) were then added. Let the cold bath warm to 21 C.Concentrated to remove DCM, then filtered solid and washed with water. 620 mg of a 70:30 mix of isomers (N-(4-chloro-5-(trifluoromethyl)pyrimidin-2-yl)-l H-pyrrolo[2,3-b]pyridin-5-amine major) was isolated. MS calcd for [C12H7C1F3N5+H]+: 314.04, found 313.80.

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 177; 178

62
[ 100960-07-4 ]
[ 3932-97-6 ]
N²-(1H-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl)pyrimidine-2,4-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
9 mg		Example 217: Preparation of N2-(lH-pyrrolo[2,3-b]pyridin-5-yl)-5-(trifluoromethyl) pyrimidine-2, -diamine2,4-Dichloro-5-(trifluoromethyl)pyrimidine (0.060 g, 0.277 mmol), 2,2- difluorocyclopropan-l -amine-HCl (0.036 g, 0.277 mmol) and N-ethyl-N-isopropylpropan-2- amine (0.096 ml, 0.553 mmol) were mixed in Acetonitrile (I ml). The mixture was microwaved at 70 C for 10 minutes and then concentrated. lH-pyrrolo[2,3-b]pyridin-5-amine (0.037 g, 0.277 mmol) and acetic acid (0.016 ml, 0.277 mmol) were added. The mixture was microwaved at 120 C for 20 minutes and then concentrated. 9 mg of side product was recovered after automated reverse phase chromatography (water- MeCN eluent). MS calcd for [C]2H9F3N6+H]+: 295.09, found 294.90.

Reference： [1]Patent: WO2016/33100,2016,A1 .Location in patent: Page/Page column 195

63
[ 100960-07-4 ]
4-(((3-chloro-1,4-dioxo-1,4-dihydronaphthalen-2-yl)amino)methyl)benzoic acid [ No CAS ]
4-((3-chloro-1,4-dioxo-1,4-dihydronaphthalen-2-ylamino)methyl)-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77.1%		A mixture of 97 (0.30 g, 0.88 mmol), HBTU (0.50 g, 1.32 mmol), DIPEA (0.23 ml, 1.32 mmol) and DMF (2.5 ml) was stirred for a while, to which was then added 5-amino7- azaindole (0.18 g, 1.32 mmol) at room temperature and the mixture was stirred overnight. The residue was filtered by suction filtration to yield a red product. The residue was filtered without further purification to afford 39 (0.31 g, 77.10 %) as a red solid.1H-NMR (300 MHz, DMSO-d6): delta 5.05 (d, J= 7.2 Hz, 2H), 6.44 (s, 1H), 7.45-7.47 (m, 3H), 7.76 (t, J= 8.1 Hz, 1H), 7.84 (t, J= 7.8 Hz, 1H), 7.93-8.00 (m, 4H), 8.12 (br, 1H), 8.31 (s, 1H), 8.44 (s, 1H), 10.23 (s, 1H), 11.57 (s, 1H).
	With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide;	[00173]A mixture of 97 (0.30 g, 0.88 mmol), HBTU (0.50 g, 1.32 mmol), DIPEA (0.23 ml, 1.32 mmol) and DMF (2.5 ml) was stirred for a while, to which was then added 5-amino7- azaindole (0.18 g, 1.32 mmol) at room temperature and the mixture was stirred overnight. The residue was filtered by suction filtration to yield a red product. The residue was filtered without further purification to afford 39 (0.31 g, 77.10 %) as a red solid.1H-NMR (300 MHz, DMSO-d6): ^5.05 (d, J= 7.2 Hz, 2H), 6.44 (s, 1H), 7.45-7.47 (m, 3H), 7.76 (t, J= 8.1 Hz, 1H), 7.84 (t, J= 7.8 Hz, 1H), 7.93-8.00 (m, 4H), 8.12 (br, 1H), 8.31 (s, 1H), 8.44 (s, 1H), 10.23 (s, 1H), 11.57 (s, 1H).

Reference： [1]Patent: WO2017/87695,2017,A1 .Location in patent: Paragraph 0098
[2]Patent: WO2017/14788,2017,A1 .Location in patent: Paragraph 00173

64
[ 100960-07-4 ]
3-bromo-7-chloro-5-hydroxy-2H-benzo[e][1,2,4]thiadiazine 1,1-dioxide [ No CAS ]
3-((1H-pyrrolo[2,3-b]pyridin-5-yl)amino)-7-chloro-5-hydroxy-4H-benzo[e][1,2,4]thiadiazine 1,1-dioxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61 mg	With potassium dihydrogenphosphate; In tert-butyl alcohol; at 50℃; for 18h;	Example 152 (2934) 3-((1 H-Pyrrolor2,3-blpyridin-5-yl)amino)-7-chloro-5-hvdroxy-4H-benzorein ,2,4 (2935) Ithiadiazine 1.1 -dioxide (2936) (2937) To a suspension of 3-bromo-7-chloro-5-hydroxy-4H-benzo[e][1 ,2,4]thiadiazine 1 ,1 -dioxide (lnt-3, 125 mg) in f-butanol (4.0 ml_) was added 1 H-pyrrolo[2,3-b]pyridin-5-amine (59 mg) and potassium dihydrogen phosphate (105 mg). The reaction was heated at 50 C for 18 h and then poured into water and acidified with 1 N aq HCI to pH 2. The resulting solids were collected by filtration, rinsed with water and ethyl ether, and then dried using air suction to afford a crude solid that was purified by reverse phase HPLC (C-18: 30x50 mm column; 20-60% acetonitrile w/ 0.1 % TFA/water w/ 0.1 % TFA) to afford the titled compound (61 mg) as a white solid. LC-MS m/z 364.0 [M+H]. NMR (400 MHz, DMSO-c/6) delta ppm 1 1 .74 (br. s., 1 H) 1 1 .65 (br. s., 1 H) 10.26 (br. s., 1 H) 9.41 (s, 1 H) 8.18 (d, J=2.28 Hz, 1 H) 8.12 (d, J=2.28 Hz, 1 H) 7.52 (t, J=2.80 Hz, 1 H) 7.17 (d, J=2.28 Hz, 1 H) 7.05 (d, J=2.28 Hz, 1 H) 6.50 (dd, J=3.42, 1 .90 Hz, 1 H).

Reference： [1]Patent: WO2017/98421,2017,A1 .Location in patent: Page/Page column 266

65
[ 100960-07-4 ]
[ 77718-46-8 ]
5-(N-(1H-pyrrolo[2,3-b]pyridin-5-yl)sulfamoyl)-2-hydroxybenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
129.8 mg	With pyridine; In dichloromethane; at 0 - 20℃; for 16.0833h;Inert atmosphere;	To a solution of 1 H-pyrrolo[2,3-b]pyridin-5-amine (0.364 mL) in DCM (15 mL) stirred under nitrogen at 0 C was added 3-carbamoyl-4-hydroxybenzene-1 -sulfonyl chloride (lnt-1 , 708 mg) portionwise over 5 min. The reaction mixture was allowed to warm to RT and stirred for 16 hr. The reaction mixture was concentrated under reduced pressure and the residue was triturated with water (3 x 15 mL), collected by filtration, washed with diethyl ether (3 x 20 mL), n-pentane (3 x 15 mL), and 10% acetonitrile in water, and dried under vacuum to obtain the crude product. This was purified by preparative HPLC (Sunfire C18, 30x150 mm) using a gradient of 10-50% acetonitrile in 0.1 % formic acid (aq). The desired fraction was concentrated under reduced pressure to remove the acetonitrile and the resulting slurry was filtered on a Buchner funnel. The precipitate was washed with water (3 x 15 mL) and dried under vacuum to afford the titled compound (129.8 mg). LCMS m/z 333.0 (M+H)+. 1H NMR (400 MHz, DMSO-c/6) delta ppm 6.38 (dd, J=3.40, 1 .86 Hz, 1 H) 7.01 (d, J=8.77 Hz, 1 H) 7.32 - 7.53 (m, 1 H) 7.62 (d, J=2A 9 Hz, 1 H) 7.66 (dd, J=8.77, 2.41 Hz, 1 H) 7.85 (d, J=2.41 Hz, 1 H) 7.91 - 8.1 1 (m, 1 H) 8.23 (d, J=2.41 Hz, 1 H) 8.48 (br. s., 1 H) 9.84 (s, 1 H) 1 1 .60 (br. s., 1 H) 13.42 (s, 1 H).

Reference： [1]Patent: WO2017/153952,2017,A1 .Location in patent: Page/Page column 140; 141

66
[ 100960-07-4 ]
(R)-(2-(2-methoxy-7-methylquinoxalin-5-yl)-7,8-dihydro-[1,4]dioxino[2',3':3,4]benzo[1,2-d]thiazol-7-yl)methyl carbonochloridate [ No CAS ]
(R)-(2-(2-methoxy-7-methylquinoxalin-5-yl)-7,8-dihydro-[1,4]dioxino[2’,3‘:3,4]benzo[1,2-d]thiazol-7-yl)methyl 1H-pyrrolo[2,3-b]pyridin-5-ylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 20℃; for 1h;	A solution of Intermediate 103A (12 mg, 0.026 mmol) in DCM (1.5 mL) was added to a suspension of 1H-pyrrolo[2,3-bjpyridin-5-amine (10.47 mg, 0.079 mmol) in DCM (0.5 mL) and DIEA (0.046 mL, 0.262 mmol). The reaction mixture was stirred atroom temperature for 1 h, at which time LCMS indicated a completion of reaction. After evaporation of solvent, the crude was dissolved in DMSO and purified via preparative LC/MS (method C, 45-100% B over 20 minutes, then a 5-minute hold at 100% B). Fractions containing the desired product were combined and dried via centrifugal evaporation to yield Example 107 (4.5 mg, 29.1% yield). ?H NMR (500MHz, DMSO-d6)oe 11.52 (br. s., 1H), 9.79 (br. s., 1H), 8.59 (s, 1H), 8.44 (s, 1H), 8.23 (br. s., 1H), 8.06 (br. s., 1H), 7.70 (s, 1H), 7.59 (d, J=8.8 Hz, 1H), 7.42 (br. s., 1H), 7.13 (d, J=8.5 Hz, 1H), 6.41 (br. s., 1H), 4.69-4.51 (m, 2H), 4.48-4.36 (m, 2H), 4.28 (br. s., 1H), 4.01 (s, 3H), 2.55 (s, 3H). LC-MS: method C, RT = 2.30 mm, MS (ESI) m/z: 555.15 (M+H) Analytical HPLC purity (method B): 94%.

Reference： [1]Patent: WO2018/13776,2018,A1 .Location in patent: Page/Page column 316

67
C₉H₁₀N₂O [ No CAS ]
[ 100960-07-4 ]

Yield	Reaction Conditions	Operation in experiment
38%	With sodium azide; methanesulfonic acid; trifluoroacetic acid; In hexane; at 40℃; for 10h;	Take a reaction tube, add 50 mg of sodium azide, 48.6 mg of 1-(1H-pyrrole[2,3-b]-5-aminopyridinyl)ethanol.300 uL of trifluoroacetic acid, 150 uL of methanesulfonic acid, 1.0 mL of n-hexane, and stirred at 40 C for 10 hours.After the reaction was completed, 10 mL of a sodium hydroxide solution was added to quench the reaction, and the mixture was extracted with ethyl acetate three times.The organic phase was washed with 5 mL of brine and the organic phases were combined.Column chromatography yielded 15.2 mg of 1H-pyrrolo[2,3-b]pyridin-5-amine in a yield of 38%.

Reference： [1]Patent: CN109134267,2019,A .Location in patent: Paragraph 0267-0269

68
[ 100960-07-4 ]
[ 2905-61-5 ]
2,5-dichloro-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With N-ethyl-N,N-diisopropylamine; In dichloromethane; for 2h;Inert atmosphere;	<strong>[100960-07-4]1H-pyrrolo[2,3-b]pyridine-5-amine</strong> (150 mg, 1.0 equiv.),DIPEA (160 mg, 1.1 equiv.) is soluble in anhydrous DCM.The freshly prepared 2,5-dichlorobenzoyl chloride (260 mg, 1.1 equiv.) was slowly added dropwise in anhydrous DCM and stirred under nitrogen for 2 hours. The TLC monitors the reaction in real time. After the reaction, diluted with water,The organic phase is extracted three times with an appropriate amount of ethyl acetate. The organic phase is washed with water, a saturated NaHCO3 solution and a saturated NaCl solution, and the organic layer is dried over anhydrous NaSO?Purification by silica gel column gave 2,5-dichloro-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)benzamide (200 mg, yield:57%).

Reference： [1]Patent: CN109232358,2019,A .Location in patent: Paragraph 0129; 0132; 0133

69
[ 100960-07-4 ]
[ 2905-61-5 ]
N-(1-benzoyl-1H-pyrrolo[2,3-b]pyridin-5-yl)-2,5-dichlorobenzamide [ No CAS ]

Reference： [1]Patent: CN109232358,2019,A

70
[ 100960-07-4 ]
3-(3-(4-(chloromethyl)benzyl)isoxazol-5-yl)pyridin-2-amine [ No CAS ]
N-(4-((5-(2-aminopyridin-3-yl)isoxazol-3-yl)methyl)benzyl)-1H-pyrrolo[2,3-b]pyridin-5-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15%	With N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 20 - 60℃; for 75h;	3-(3-(4-(Chloromethyl)benzyl)isoxazol-5-yl)pyridin-2-amine (Intermediate B, 0.10 g, 0.33 mmol) and lH-pyrrolo[2,3-b]pyridin-5-amine (0.22 g, 1.7 mmol), were dissolved in tetrahydrofiiran. Diisopropylethylamine (0.14 mL, 0.80 mmol) was added and the heterogenous mixture was stirred at room temperature for 3 hours, and then heated at 60 C for 72 hours. The mixture was cooled to room temperature and extracted three times with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate and evaporated under reduced pressure. The obtained residue was purified using Biotage reverse phase flash chromatography (l2g C18 SNAP, 5-95% acetonitrile in water with 0.1% formic acid). The desired fraction was lyophilized to give the title compound as a white solid (20 mg, 0.051 mmol, 15%). MS: 397.3 [M+H]+.

Reference： [1]Patent: WO2019/113542,2019,A1 .Location in patent: Paragraph 0351; 0352

71
[ 100960-07-4 ]
[ 5617-70-9 ]
2-oxo-1-{1H-pyrrolo[2,3-b]pyridin-5-yl}pyrrolidine-3-carboxylic acid [ No CAS ]