[ CAS No. 156270-06-3 ] {[proInfo.proName]}

Name: 156270-06-3|1H-Pyrrolo[2,3-b]pyridine-3-carboxylicacid|97%
Brand: Ambeed
SKU: A163883
Price: 5.0 USD
Availability: InStock
Rating: 96 (32 reviews)

,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

DV 2D 3D

3d Animation Molecule Structure of 156270-06-3

Structure of 156270-06-3 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 156270-06-3 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 156270-06-3 ]

SDS Specification

Alternatived Products of [ 156270-06-3 ]

Product Details of [ 156270-06-3 ]

CAS No. :	156270-06-3	MDL No. :	MFCD07778360
Formula :	C₈H₆N₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	KYBIRFFGAIFLPM-UHFFFAOYSA-N
M.W :	162.15	Pubchem ID :	10154191
Synonyms :

Calculated chemistry of [ 156270-06-3 ]

Physicochemical Properties

Num. heavy atoms :	12
Num. arom. heavy atoms :	9
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	3.0
Num. H-bond donors :	2.0
Molar Refractivity :	43.05
TPSA :	65.98 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.69 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.83
Log Po/w (XLOGP3) :	0.84
Log Po/w (WLOGP) :	1.26
Log Po/w (MLOGP) :	0.58
Log Po/w (SILICOS-IT) :	1.38
Consensus Log Po/w :	0.98

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-1.86
Solubility :	2.22 mg/ml ; 0.0137 mol/l
Class :	Very soluble
Log S (Ali) :	-1.81
Solubility :	2.52 mg/ml ; 0.0155 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-2.27
Solubility :	0.863 mg/ml ; 0.00532 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.24

Safety of [ 156270-06-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 156270-06-3 ]

* 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 [ 156270-06-3 ]
Downstream synthetic route of [ 156270-06-3 ]

[ 156270-06-3 ] Synthesis Path-Upstream 1~13

1
[ 1065100-83-5 ]
[ 156270-06-3 ]

Yield	Reaction Conditions	Operation in experiment
94.3%	With potassium permanganate In dichloromethane at 50℃; for 3 h;	(2) Add 7-azaindole-3-methanol to dichloromethane, heat to 50°C, add KMnO4 and mix well.The reaction was stirred for 3 h, filtered, evaporated under reduced pressure, and recrystallized to give 7-azaindole-3-carboxylic acid.In step (1), 7-azaindole and water are used in a molar ratio of 1 mol/L; 7-azaindole and tetramethylguanidine are used in a molar ratio of 2:5;The mass ratio of 7-azaindole to MFI zeolite is 6:7;The molar ratio of 7-azaindole to formaldehyde is 1:1.2;The microwave radiation power is 300W.The molar ratio of 7-azaindole-3-methanol to KMnO4 used in step (2) is 12:15.The yield of 7-azaindole-3-carboxylic acid produced was 94.3percent and the purity was 99.3percent.

Reference： [1] Patent: CN107903261, 2018, A, . Location in patent: Paragraph 0021-0031; 0035-0038; 0042-0045; 0049-0059

2
[ 4649-09-6 ]
[ 156270-06-3 ]

Reference： [1] Patent: WO2006/50976, 2006, A1, . Location in patent: Page/Page column 31
[2] Patent: WO2004/111048, 2004, A1, . Location in patent: Page 40

3
[ 163220-69-7 ]
[ 156270-06-3 ]

Reference： [1] Patent: WO2008/5457, 2008, A2, . Location in patent: Page/Page column 73

4
[ 4414-89-5 ]
[ 156270-06-3 ]

Reference： [1] Chinese Chemical Letters, 2011, vol. 22, # 3, p. 272 - 275
[2] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213
[3] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213

5
[ 269726-49-0 ]
[ 156270-06-3 ]

Reference： [1] Chinese Chemical Letters, 2011, vol. 22, # 3, p. 272 - 275
[2] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213

6
[ 269726-48-9 ]
[ 156270-06-3 ]

Reference： [1] Chinese Chemical Letters, 2011, vol. 22, # 3, p. 272 - 275
[2] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213

7
[ 269726-50-3 ]
[ 156270-06-3 ]

Reference： [1] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213
[2] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213

8
[ 271-63-6 ]
[ 156270-06-3 ]

Reference： [1] Chemische Berichte, 1943, vol. 76, p. 128,134
[2] Patent: WO2008/5457, 2008, A2,

9
[ 108-24-7 ]
[ 156270-06-3 ]

Reference： [1] Journal of the American Chemical Society, 1956, vol. 78, p. 1247,1249

10
[ 271-63-6 ]
[ 76-02-8 ]
[ 156270-06-3 ]

Reference： [1] Organic Process Research and Development, 2003, vol. 7, # 2, p. 209 - 213

11
[ 67-56-1 ]
[ 156270-06-3 ]
[ 808137-94-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	Stage #1: at 36℃; for 0.25 h; Stage #2: at 50℃; for 0.75 h;	This example relates to a process for the synthesis of methyl 1-pyrrolo [2,3-b] pyridine-3-carboxylate, 1 mol of lH-pyrrolo [2,3-b] pyridine-3-carboxylic acid and 4 mol of methanol were charged into a 1 L three-necked flask, The molar ratio of 1 H-pyrrolo [2,3-B] pyridine-3-carboxylic acid to methanol was 1: 4, heated at 36 ° C for 15 minutes, Then, a mixture consisting of 0. 7 mol of anhydrous calcium chloride and 0.5 mol of nano-sized aluminum oxide was added as a catalyst, Pyrrolo [2,3-B] pyridine-3-carboxylic acid, anhydrous calcium chloride, The molar ratio of nano-Al2O3 was 1: 0.7: 0.5, and the mixture was refluxed at 50 ° C for 45 minutes to carry out esterification reaction, Cooled to room temperature, filtered, The filtrate was evaporated at 60 ° C under reduced pressure to remove the excess methanol to give methyl 1H-pyrrolo [2,3-b] pyridine-3-carboxylate as a white solid in 87percent yield and HPLC purity 98.7percent.

Reference： [1] Patent: CN105218546, 2016, A, . Location in patent: Paragraph 0017; 0018

12
[ 156270-06-3 ]
[ 808137-94-2 ]

Reference： [1] Patent: WO2004/111048, 2004, A1, . Location in patent: Page 40

13
[ 156270-06-3 ]
[ 18107-18-1 ]
[ 808137-94-2 ]

Reference： [1] Patent: WO2008/5457, 2008, A2, . Location in patent: Page/Page column 78

[ 156270-06-3 ] Synthesis Path-Downstream 1~65

1
[ 271-63-6 ]
[ 156270-06-3 ]

Reference： [1]Chemische Berichte,1943,vol. 76,p. 128,134
[2]Patent: WO2008/5457,2008,A2
[3]European Journal of Medicinal Chemistry,2019,vol. 180,p. 291 - 309

2
1H-pyrrolo[2,3-b]pyridine-3-carbaldehyde oxime [ No CAS ]
[ 108-24-7 ]
[ 156270-06-3 ]

Reference： [1]Journal of the American Chemical Society,1956,vol. 78,p. 1247,1249

3
[ 163220-69-7 ]
[ 156270-06-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium hydroxide; In water; at 20℃; for 6h;	A suspension of 67 (3.0 g, 11.4 mmol) in aqueous sodium hydroxide (3 M, 65 mL, 200 mmol) was stirred at room temperature for 6 h. The solution was acidified with aqueous hydrochloric acid (6 M) and the precipitate obtained by filtration. The solid was dried in vacuo to obtain the title compound 68 (1.8 g, 100%) as an off-white powder, the spectroscopic data of which corresponded to previously described [39].
		Compound 23.1 (2.5 g, 9.51 mmol) was dissolved in 25 ml 20% aqueous KOH solution while stirring. After two hours, the solution was adjusted to pH 2 with concentrated HCl. A white precipitate formed at this stage. The solid was separated by centrifugation, washed with copious water and dried to give Compound 26.1 (1.63 g) as a white solid. ES (+) MS m/e = 163 (M+l).

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 180,p. 291 - 309
[2]Patent: WO2008/5457,2008,A2 .Location in patent: Page/Page column 73

4
[ 156270-06-3 ]
[ 870-46-2 ]
[ 1001413-24-6 ]

Yield	Reaction Conditions	Operation in experiment
42%	With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃;	Compound 26.1 (5.72 g, 35.3 mmol), l-(3-Dimethylarninopropyl)-3- ethylcarbodiimide hydride (6.77 g, 35.3 mmol) and 1-hydroxybenzotriazole hydrate (5.4 g, 35.3 mmol) were suspended in 90 ml DMF. Then tert-bvAyl carbazate (4.67 g, 35.3 mmol) was added followed by diisopropylethylamine (12.3 ml, 70.6 mmol). The reaction was stirred overnight at <n="76"/>room temperature. Then the solvent was removed under vacuum and the residue was flooded with ethyl acetate, rinsed with saturated sodium bicarbonate, brine, dried over sodium sulfate, filtered, and evaporated to dryness. This was purified using flash chromatography to give Compound 26.2 (4.06 g, 42percent) as a white solid. ES (+) MS m/e = 277 (M+l).

Reference： [1]Patent: WO2008/5457,2008,A2 .Location in patent: Page/Page column 73-74

5
[ 156270-06-3 ]
[ 18107-18-1 ]
[ 808137-94-2 ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; hexane; toluene; at 0 - 20℃; for 1h;Product distribution / selectivity;	Compound 26.1 (0.81 g, 5 mmol) was suspended in a mixture of MeOH and toluene (10 ml, 1 :3) and chilled in ice-water bath. A solution of 2 M (trimethylsilyl) diazomethane in hexanes (3 ml, 6 mmol) was added dropwise. The reaction was then removed from the ice-water bath, allowed to warm to room temperature, and stirred for 1 hour. The reaction was evaporated and co-evaporated with DCM a couple times to give Compound 31.2 (785 mg). ES (+) MS m/e = 177 (M+l).

Reference： [1]Patent: WO2008/5457,2008,A2 .Location in patent: Page/Page column 78

6
[ 156270-06-3 ]
[ 808137-94-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuric acid; In methanol; at 20℃; for 16h;Heating / reflux;	4.22 g (26 mmol) of <strong>[156270-06-3]1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid</strong> were added to 100 cm3of methanol at a temperature in the region of 20C and then 2.5 cm3 of concentratedsulfuric acid were run in dropwise. After stirring at reflux of the solvent for 16 h, thereaction medium was concentrated to dryness under reduced pressure (2.7 kPa). Theresidue was rapidly added to 50 cm3 of water and the pH was adjusted to 8 by additionof 1N sodium hydroxide. After extracting with 300 cm3 of ethyl acetate, the organicphase was washed with 2 times 100 cm3 of water and then 100 cm3 of saturatedaqueous sodium chloride solution. After drying over magnesium sulfate and thenconcentrating to dryness under reduced pressure (2.7 kPa), 3.7 g of methyl 1H-pyrrolo[2,3-b]pyridine-3-carboxylate were obtained in the form of a yellow powder.Mass spectrum: El: m/z = 176 M+; base pic: m/z = 145 (M-CH3O)+.

Reference： [1]Patent: WO2004/111048,2004,A1 .Location in patent: Page 40

7
[ 4649-09-6 ]
[ 156270-06-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium chlorite; sodium dihydrogenphosphate; 2-methyl-but-2-ene; In 1,4-dioxane; water; at 20℃; for 15h;	2.3 g (15.7 mmol) of 1H-pyrrolo[2,3-b]pyridine-3-carboxaldehyde and 23 cm3(217 mmol) of 2-methyl-2-butene were added to 120 cm3 of dioxane at a temperatureof 20C and then a solution of 2.7 g (30 mmol) of sodium chlorite and 9.2 g(66.7 mmol) of monosodium phosphate in 100 cm3 of water was run in. After stirring ata temperature in the region of 20C for 15 h, the reaction mixture was concentrated todryness under reduced pressure (2.7 kPa). The residue was taken up in 50 cm3 ofwater, filtered off, rinsed with 3 times 30 cm3 of water and then dried under a hood for16 h. 2.2 g of 1 H-pyrrolo[2,3-b]pyridine-3-carboxylic acid were thus obtained in theform of a white powder. Mass spectrum: El: m/z = 162 M+ base peak

Reference： [1]Patent: WO2006/50976,2006,A1 .Location in patent: Page/Page column 31
[2]Patent: WO2004/111048,2004,A1 .Location in patent: Page 40

8
[ 156270-06-3 ]
trans-3-(2-(1-(4-amino)cyclohexyl)ethyl)-7-cyano-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]
trans-7-cyano-3-(2-(1-(4-(3-pyrrolo[2,3-b]pyridyl)carboxamido)cyclohexyl)ethyl)-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride;benzotriazol-1-ol; In dichloromethane; at 20℃; for 16h;	A mixture of trans-3- (2- (1- (4-amino) cyclohexyl) ethyl)-7-cyano-2, 3,4, 5-tetrahydro- 1 H 3-benzazepine (103 mg, 0.35 mmol), 3-pyrrol [2,3-b] pyridyl carboxylic acid (56 mg, 0.35 mmol), 1- (3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (67 mg, 0.35 mmol) and 1-hydroxybenzotriazole (20 mg, 0.15 mmol) in dichloromethane (8 ml) was shaken at room temperature for 16 h. The reaction mixture was washed with saturated aqueous sodium bicarbonate (4 ml). The resulting precipitate was collected by filtration, washed with water (2 x 10 ml) and dried to give the title compound (81 mg, 0.18 mmol, 53percent) as a colourless solid. Mass spectrum (API+) : Found 442 (MH+). C27H31N5O requires 441. 1 H NMR (DMSO-d6) 8 : 1.02 (2H, m), 1.15-1. 45 (6H, m), 1.81 (4H, m), 2.50 (5H, m), 2.91 (4H, m), 3.73 (1H, m), 7.14 (1H, m), 7.32 (1H, d, J = 8 Hz), 7.57 (2H, m), 7.73 (1H, d, J = 8 Hz), 8.16 (1H, m), 8.25 (1H, m), 8.42 (1H, m), 12.03 (1H, br s).

Reference： [1]Patent: WO2005/94835,2005,A1 .Location in patent: Page/Page column 72-73

9
[ 156270-06-3 ]
trans-3-(2-(1-(4-amino)cyclohexyl)ethyl)-7-(5-(3-methyl)-1,2,4-oxadiazolyl)-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]
trans-7-(5-(3-methyl)-1,2,4-oxadiazolyl)-3-(2-(1-(4-(3-pyrrolo[2,3-b]pyridyl)carboxamido)cyclohexyl)ethyl)-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride;benzotriazol-1-ol; In DMF (N,N-dimethyl-formamide); dichloromethane; at 20℃; for 16h;	A mixture of trans-3- (2- (1- (4-amino) cyclohexyl)-7- (5- (3-methyl)-1, 2, 4-oxadiazolyl)- 2,3, 4, 5-tetrahydro-1 H-3-benzazepine (21.0 g, 59.3 mmol), pyrrolo [2,3-b] pyridyl-3- carboxylic acid (10.57 g, 65.2 mmol), EDC hydrochloride (12.46 g, 64.4 mmol) and HOBT (0.5 g) in CH2CI2 (630 ml) and DMF (84 ml) was stirred at ambient temperature for 16 h. Saturated aqueous sodium bicarbonate (350 ml) was added and the mixture stirred for 0.25 h. The precipitate was collected by filtration, washed in turn with water and diethyl ether and dried in vacuo to give the free base of the title compound (18.0 g, 61 percent). Mass spectrum (API+) : Found 499 (MH+). C29H34N602 requires 498. NMR (DMSO-d6) 8 : 0.90-1. 10 (2H, m), 1.10-1. 40 (5H, m), 1.70-1. 90 (4H, m), 2.40-2. 70 (6H, m), 2.96 (3H, s), 3.31 (4H, m), 3.89 (1H, m), 7.15 (1H, m), 7.36 (1 H, d, J = 8 Hz), 7.71 (1 H, d, J = 8 Hz), 7.75-7. 85 (2H, m), 8.12 (1 H, s), 8.20 (1 H, s), 8.35 (1 H, d, J = 8 Hz), 12.02 (1 H, br s).

Reference： [1]Patent: WO2005/94835,2005,A1 .Location in patent: Page/Page column 61; 78-79

10
[ 156270-06-3 ]
[ 148703-15-5 ]
[ 156270-11-0 ]

Yield	Reaction Conditions	Operation in experiment
35%	With methyllithium; In tetrahydrofuran; methanol; thionyl chloride; diethyl ether; chloroform; water;	a) 7-Azaindole-3-carboxylic acid (100 mg, 0.617 mmol) was stirred in thionyl chloride (8 ml) under nitrogen for 4 h. The solvent was removed in vacuo to afford crude acid chloride. Methyl lithium (1.5M in diethylether, 0.4 ml) was added dropwise to a cooled (0° C.) solution of 1-butyl-4-piperidine-methanol (0.110 g, 0.643 mmol) in dry THF (5 ml) under nitrogen atmosphere. Stirring was continued for 10 minutes. A solution of the acid chloride in dry THF (10 ml) was added and stirring continued overnight. Water was added and the solvent concentrated in vacuo. The residue was partitioned between chloroform and water. The organic phase was dried (Na2 SO4) filtered and concentrated. The residue was chromatographed on silica using chloroform and methanol as eluant to afford (1-butyl-4-piperidinylmethyl 7-azaindole-3-carboxylate as a yellow solid (69 mg, 35percent) 1 H NMR (250 MHz, CDCl13)

Reference： [1]Patent: US5696129,1997,A

11
[ 156270-06-3 ]
[ 1263816-09-6 ]

Reference： [1]Journal of Organic Chemistry,2011,vol. 76,p. 1177 - 1179

12
[ 156270-06-3 ]
[ 22007-68-7 ]
C₁₂H₁₄N₄O [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2011,vol. 76,p. 1177 - 1179

13
[ 156270-06-3 ]
[ 310887-39-9 ]

Yield	Reaction Conditions	Operation in experiment
71%	With hydrazine hydrate; In 1,4-dioxane; at 100℃; for 12h;	Example of Step 1: Preparation of the Hydrazides (for Example Precursor 1 for "A2"); 1.40 g of 1-(<strong>[156270-06-3]1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid</strong>, 3.8 ml of hydrazine hydrate in 1 ml of dioxane are stirred at 100° C. for 12 hours in a reaction vessel. On cooling, a colourless solid is formed, which is filtered off with suction, washed with water and dried, giving 1.05 g of 1-(1H-pyrrolo[2,3-b]-pyridine-3-carbonhydrazide (71percent yield); MS-FAB (M+H+)=177.1; Rf (polar method): 0.70 min.

Reference： [1]Patent: US2011/166175,2011,A1 .Location in patent: Page/Page column 23

14
[ 156270-06-3 ]
[ 1210437-54-9 ]

Reference： [1]Patent: US2011/166175,2011,A1

15
[ 156270-06-3 ]
[ 1210437-67-4 ]

Reference： [1]Patent: US2011/166175,2011,A1

16
[ 156270-06-3 ]
[ 1210437-57-2 ]

Reference： [1]Patent: US2011/166175,2011,A1

17
[ 156270-06-3 ]
[ 1041481-60-0 ]
[ 1210437-79-8 ]

Yield	Reaction Conditions	Operation in experiment
	With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In N,N-dimethyl-formamide; at 20℃; for 72h;	EXAMPLE; 200 mg of 1-(<strong>[156270-06-3]1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid</strong>, 260.5 mg of 4-(3-methoxybenzyl)thiosemicarbazide, 230 mg of HOBT and 288 mg of DAPECI in 3 ml of DMF are stirred at RT for 3 days in a screw-lid vial. The batch is poured onto water, and the resultant precipitate is filtered off with suction and dried, giving 250 mg of coupling product [57percent, MS-FAB (M+H+)=356.4; Rf (polar method): 1.60 min], which can be employed for the cyclisation without further purification.

Reference： [1]Patent: US2011/166175,2011,A1 .Location in patent: Page/Page column 24

18
[ 269726-49-0 ]
[ 156270-06-3 ]

Reference： [1]Chinese Chemical Letters,2011,vol. 22,p. 272 - 275
[2]Organic Process Research and Development,2003,vol. 7,p. 209 - 213

19
[ 4414-89-5 ]
[ 156270-06-3 ]

Reference： [1]Chinese Chemical Letters,2011,vol. 22,p. 272 - 275
[2]Organic Process Research and Development,2003,vol. 7,p. 209 - 213
[3]Organic Process Research and Development,2003,vol. 7,p. 209 - 213

20
[ 269726-48-9 ]
[ 156270-06-3 ]

Reference： [1]Chinese Chemical Letters,2011,vol. 22,p. 272 - 275
[2]Organic Process Research and Development,2003,vol. 7,p. 209 - 213

21
[ 156270-06-3 ]
[ 1273122-75-0 ]