208580-23-8|Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate| Ambeed

Size	Price	VIP Price	US Stock	Global Stock	In Stock
{[ item.pr_size ]}		Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}

US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days

{[ item.pr_size ]}

In Stock

- +

Please Login or Create an Account to: See VIP prices and availability

US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks

Quality Control of [ 208580-23-8 ] Purity: 95% SDS Specification

COA

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

NMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

CNMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

HPLC

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

LC-MS

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

1-2 Day Shipping
High Quality
Technical Support

Product Details of [ 208580-23-8 ]

CAS No. :	208580-23-8
Formula :	C₁₂H₁₀BrNO₃
M.W :	296.12
SMILES Code :	O=C(C1=CNC2=C(C=CC(Br)=C2)C1=O)OCC
MDL No. :	MFCD09746289
InChI Key :	WJFBKTAITAHHAR-UHFFFAOYSA-N
Pubchem ID :	683685

Safety of [ 208580-23-8 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302-H315-H319-H335
Precautionary Statements:	P261-P280-P301+P312-P302+P352-P305+P351+P338

Application In Synthesis of [ 208580-23-8 ]

* 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.

Downstream synthetic route of [ 208580-23-8 ]

[ 208580-23-8 ] Synthesis Path-Downstream 1~36

1
[ 208580-23-8 ]
[ 206257-41-2 ]

Yield	Reaction Conditions	Operation in experiment
76%	With thionyl chloride; In N,N-dimethyl-formamide;Reflux;	j00381j Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate (5.11 g, 17.3 mmol) was dissolved in thionyl chloride (70 mL), and DMF (0.5 mL) was added. The reactionmixture was heated to reflux overnight. The resulting solution was concentrated to provide a residue, and the residue was carefully treated with a saturated sodium carbonate solution. The resulting mixture was slurried, and then filtered. The solid isolated by filtration was washed with water, and dried in a vacuum oven to produce a yellow solid. The yellow solid was then loaded onto silica gel and purified by MPLC eluting with a gradient of 5-80% ethyl acetate inhexanes to afford ethyl 7-bromo-4-chloroquinoline-3-carboxylate as a white solid (4.12 g,76%).
76%	With thionyl chloride; In N,N-dimethyl-formamide;Reflux;	Ethyl 7-bromo-4-oxo- , - y roqu no ne-3-carboxylate (5.11 g, 17.3 mmol) was dissolved in thionyl chloride (70 mL), and DMF (0.5 mL) was added. The reaction mixture was heated to reflux overnight. The resulting solution was concentrated to provide a residue, and the residue was carefully treated with a saturated sodium carbonate solution. The resulting mixture was slurried, and then filtered. The solid isolated by filtration was washed with water, and dried in a vacuum oven to produce a yellow solid. The yellow solid was then loaded onto silica gel and purified by MPLC eluting with a gradient of 5-80% ethyl acetate in hexanes to afford ethyl 7-bromo-4-chloroquinoline-3-carboxylate as a white solid (4.12 g, 76%).
75%	With trichlorophosphate; for 2h;Reflux;	General procedure: The quinoline derivate was dispersed in POCl3 (1 mL/mmol) andheated to reflux. After 2 h the reaction mixture was poured onto ice,neutralized with satd. NaHCO3, extracted with CH2Cl2 (3×12 mL/mmol), washed with brine (1×12 mL/mmol), dried over Na2SO4, filteredand evaporated. The residue was purified by FC (gradient of 5%-15% EtOAc in LP to give the desired product.5.1.4.1. Ethyl 7-bromo-4-chloroquinoline-3-carboxylate (13a). Thechloro quinoline 13a (colorless solid, 400 mg, 75%) was obtainedfrom 12a (500 mg, 1.7 mmol) according to general procedure C; m.p.91-92 C; 1H NMR (400 MHz, DMSO-d6) delta 1.38 (t, J=7.1 Hz, 3H), 4.43(q, J=7.1 Hz, 2H), 8.00 (dd, J=9.0, 2.0 Hz, 1H), 8.30 (dd,J=9.0,1H), 8.39 (d, J=2 Hz, 1H), 9.17 (s, 1H); 13C NMR (101 MHz,DMSO-d6) delta 14.0, 62.1, 123.6, 124.3, 126.2, 127.1, 131.4, 132.2, 141.9, 149.3, 150.9, 163.6.

References: [1]Patent: WO2015/131035,2015,A1 .Location in patent: Paragraph 00381.
[2]Patent: WO2015/171610,2015,A2 .Location in patent: Paragraph 000357.
[3]Bioorganic and Medicinal Chemistry,2019,vol. 27,p. 3167 - 3178.
[4]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 2155 - 2158.
[5]Nucleosides, nucleotides and nucleic acids,2004,vol. 23,p. 735 - 748.

2
[ 208580-23-8 ]
[ 236112-27-9 ]

References: [1]Nucleosides, nucleotides and nucleic acids,2004,vol. 23,p. 735 - 748.

3
[ 208580-23-8 ]
7-bromo-2-(4-bromophenyl)-5-β-D-ribofuranosyl-2H-pyrazolo[4,3-c]quinolin-3(5H)-one [ No CAS ]

References: [1]Nucleosides, nucleotides and nucleic acids,2004,vol. 23,p. 735 - 748.

4
[ 208580-23-8 ]
[ 774586-02-6 ]

References: [1]Nucleosides, nucleotides and nucleic acids,2004,vol. 23,p. 735 - 748.

5
[ 208580-23-8 ]
[ 705965-94-2 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 2155 - 2158.

6
[ 208580-23-8 ]
4-(2,4-Dichloro-phenylamino)-7-((E)-2-pyridin-4-yl-vinyl)-quinoline-3-carboxylic acid [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 2155 - 2158.

7
[ 208580-23-8 ]
4-(2,4-Dichloro-phenylamino)-7-((E)-2-pyridin-4-yl-vinyl)-quinoline-3-carboxylic acid ethyl ester [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2004,vol. 14,p. 2155 - 2158.

8
[ 351893-47-5 ]
[ 208580-23-8 ]

Yield	Reaction Conditions	Operation in experiment
88%	In diphenylether; at 235℃; for 1h;Inert atmosphere;	General procedure: The malonate derivates 11a-d were dispersed in diphenylether(1.7 mL/mmol), flushed with argon and heated to 235 C for 1 h with aheating jacket. The reaction mixture was poured into petroleum ether,the formed precipitate was collected by filtration and washed with amixture of LP/EtOAc 1/1 to yield the desired product.5.1.3.1. Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate (12a).12a (colorless solid, 5 g, 88%) was obtained from 11a (5.03 g,29 mmol) according to general procedure B; m.p. > 300 C; 1H NMR(600 MHz, DMSO-d6) delta 1.27 (t, J=7.1 Hz, 3H), 4.21 (q, J=7.1 Hz,2H), 7.57 (dd, J=8.6, 1.9 Hz, 1H), 7.82 (d, J=1.9 Hz, 1H), 8.06 (d,J=8.6 Hz, 1H), 8.58 (s, 1H), 12.31 (s, 1H); 13C NMR (151 MHz,DMSO-d6) delta 14.8, 60.2, 110.9, 121.5, 126.2, 126.6, 128.2, 128.4, 140.5,146.0, 165.0, 173.3.
69.3%	With diphenyl ether-biphenyl eutectic; at 250℃;	Dowtherm (50 niL) was taken in double neck round bottom flask (100 rnL) and heated to 2500C in sand bath. At this temperature diethyl [(3- bromophenyl)amino]methylidene}propanedioate (Intermediate 32, 10.0 g, 29.2 mmol) was added and the reaction temperature was maintained for another 1 h at 250 0C. After completion of the reaction, the reaction mixture was cooled to room temperature, a white solid was collected by filtration and dried to yield 6.0 g (69.3%) ethyl 7-bromo-4-oxo-l,4- dihydroquinoline-3-carboxylate.1H NMR (400 MHz. DMSO-d): 1.07 (t, 3H), 1.22 (s, 12H), 3.16 (q, 2H), 7.29 (m, IH), 7.31 (d, 2H), 7.61 (s, IH), 7.88 (s, IH), 8.31 (s, IH), 8.65 (s, IH), 9.44 (s, IH).
42%	In diphenylether; for 0.5h;Inert atmosphere; Reflux;	3 mL of diphenyl ether was vigorously stirred in a test tube and heated to reflux with a sand bath, and to which, 800 mg (2.35 mmol) of starting material (22) was added. The resulting solution was refluxed for another 30 min, cooled to rt, and triturated with diethyl ether to give the product as a precipitation, which was collected by filtration. The solid was washed with diethyl ether for several times to give 497 mg of white powder as the crude product, which is sufficiently pure for the further coupling reactions. For analytical purpose, the crude product was washed with 20% MeOH in DCM for three times by means of centrifuge. The resulting solid was dissolved in a minimum amount of boiling DMSO, and then cooled to rt to give the pure product as a white powder 24 (291 mg, 0.99 mmol, 42%). 1H NMR (400 MHz, DMSO-d6, measured at 100 C due to solubility issue) delta 11.88 (s, 1H, NH), 8.45 (s, 1H, H-2), 8.07 (d, J = 8.6 Hz, 1H, Haryl), 7.80 (d, J = 1.7 Hz, 1H, Haryl), 7.51 (dd, J = 8.6, 1.7 Hz, 1H, Haryl), 4.24 (q, J = 7.1 Hz, 2H, Et), 1.29 (t, J = 7.1 Hz, 3H, Et). 13C NMR (100 MHz, DMSO-d6, measured at 100 C due to solubility issue) delta 173.17(CO), 164.99(CO), 145.27(C-2), 140.86(Cq,aryl), 128.36(CHaryl), 127.94(CHaryl), 126.76(Cq,aryl), 126.00(Cq,aryl), 121.55(CHaryl), 112.01(Cq,aryl), 60.03(Et), 14.62(Et); HRMS (ESI-) calcd for C12H9BrNO3-(M-H+) 293.9771, found 293.9772; HPLC: Solubility is too poor to make an HPLC analysis; Mp: 334-335 C (decomp., recrystallized from DMSO).

	With Dowtherm A; for 0.5h;Reflux;	General procedure: A solution of the appropriate meta or para-substituted anilines (100 mmol), 20.4 mL (100 mmol) of diethyl ethoxymethylenemalonate and 20 mL of ethanol was heated under reflux for 2 hours. The mixture was allowed to cool and then was poured into ice-cold water. The precipitate was collected by filtration and the corresponding enamine-type derivatives (3.0 g) were refluxed for 30 minutes in 30 mL of Dowtherm A, leading to crude oxoquinolines 4 that were recrystallized from dimethylformamide.
	In diphenylether; at 210℃;Microwave irradiation;	General procedure: A solution of theappropriate aniline derivative (1 eq) in toluene (20-50 mL) was treated withdiethyl 2-(ethoxymethylene)malonate (1.2 eq) and was refluxed for 15-20 h. Thesolvent was removed under reduced pressure and the crude product wasrecrystallized from n-hexane at -20 C.After that, the resulting diethyl (2-(amino)methylene)malonate was dissolved in5-10 mL diphenyl ether and was reacted for 20-60 min at 210 C undermicrowave irradiation.
	at 250℃; for 1h;	Intermediate 55Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylateDowtherm (50 mL) was taken in double neck round bottom flask (100 mL) and heated to 250 C. in sand bath. At this temperature diethyl [(3-bromophenyl)amino]methylidene}propanedioate (Intermediate 54, 10.0 g, 29.2 mmol) was added and the mixture was maintained at 250 C. for another 1 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solid was collected by filtration and dried to yield 6.0 g (69.3%) ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate as the predominant isomer.1H NMR (400 MHz, DMSO-d6): delta 1.07 (t, 3H), 1.22 (s, 12H), 3.16 (q, 2H), 7.29 (m, 1H), 7.31 (d, 2H), 7.61 (s, 1H), 7.88 (s, 1H), 8.31 (s, 1H), 8.65 (s, 1H), 9.44 (s, 1H).LC-MS: m/z 294 (M+H).

References: [1]Bioorganic and Medicinal Chemistry,2019,vol. 27,p. 3167 - 3178.
[2]Journal of Medicinal Chemistry,2015,vol. 58,p. 5522 - 5537.
[3]Patent: WO2009/147433,2009,A1 .Location in patent: Page/Page column 279.
[4]Bioorganic and Medicinal Chemistry,2012,vol. 20,p. 4790 - 4800.
[5]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 1010 - 1013.
[6]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 5055 - 5058.
[7]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 4597 - 4601.
[8]Journal of Medicinal Chemistry,2015,vol. 58,p. 560 - 576.
[9]European Journal of Medicinal Chemistry,2018,vol. 152,p. 377 - 391.
[10]Patent: US2010/317624,2010,A1 .Location in patent: Page/Page column 63.
[11]European Journal of Medicinal Chemistry,2019,vol. 178,p. 154 - 167.

9
[ 25561-30-2 ]
[ 208580-23-8 ]
C₁₅H₁₈BrNO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With chloro-trimethyl-silane; In acetonitrile; at 60 - 70℃; for 3h;Inert atmosphere;	General procedure: A stirred solution of 1,4-dihydro-4-oxo-quinolines 4 (4.0 mmol), anhydrous acetonitrile (5.0 mL) and BSTFA (3.0 mL, 11.2 mmol) containing 1% of trimethylchlorosilane (TMCS), was heated at 60-70 oC, under nitrogen, for 3 h. The resulting mixture was allowed to cool to room temperature and a solution of 1-O-acetyl-2,3,5-tri-O-benzoyl-beta-D-ribofuranose (2.020 g, 4 mmol) in 15 mL of acetonitrile was added, followed by dropwise addition of TMSOTf (0.4 mL, 2.09 mmol). After having been stirred for 4 h, at room temperature, the solution was poured into ice-cold water (20 g), and neutralized with saturated aqueous sodium bicarbonate solution. The resulting mixture was extracted with methylene chloride (3 x 20 mL) and the combined organic layers were washed with water (3 x 20 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to leave the corresponding products as white crystals, which were recrystallized from ethanol to produce the protected ribonucleosides.

References: [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 1010 - 1013.
[2]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 4597 - 4601.

10
[ 74-96-4 ]
[ 208580-23-8 ]
[ 131993-96-9 ]

Yield	Reaction Conditions	Operation in experiment
68.8%		Intermediate 56Ethyl 7-bromo-1-ethyl-4-oxo-1,4-dihydroquinoline-3-carboxylateEthyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate (Intermediate 55, 1.0 g, 3.3 mM) was dissolved in dimethylformamide (20 mL) and potassium carbonate (1.39 g, 10.1 mM) was added. After stirring the mixture for 10 min, ethyl bromide (0.76 mL, 10.1 mM) was added, and the reaction mixture was heated to 80 C. for 3 h. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered through celite, and concentrated under reduced pressure to dryness. The residue was diluted with diethyl ether to obtain a solid which was filtered and dried to afford 750 mg (68.8%) of ethyl 7-bromo-1-ethyl-4-oxo-1,4-dihydroquinoline-3-carboxylate as white solid.1H NMR (400 MHz, DMSO-d6):delta 1.26 (t, 3H), 1.34 (t, 3H), 4.21 (q, 2H), 4.42 (q, 2H), 7.64 (d, 1H), 8.06 (s, 1H), 8.25 (d, 1H), 8.68 (s, 1H).LC-MS: m/z 324 (M+H).

References: [1]Patent: US2010/317624,2010,A1 .Location in patent: Page/Page column 63.
[2]Tetrahedron,2011,vol. 67,p. 7336 - 7342.

11
[ 1192-80-9 ]
[ 208580-23-8 ]
[ 1258213-54-5 ]

Yield	Reaction Conditions	Operation in experiment
89.13%	With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 2h;	Intermediate 51Ethyl 7-bromo-1-[(5-methyl-1,2,4-oxadiazol-3-yl)methyl]-4-oxo-1,4-dihydroquinoline-3-carboxylateTo a stirred solution of <strong>[208580-23-8]ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate</strong> (Intermediate 55, 3.5 g, 11.82 mmol) in dry dimethylformamide (40 mL), potassium carbonate (4.90 g, 85.47 mM) was added and stirred at room temperature. To the above reaction mixture 3-chloromethyl-5-methyl-1,2,4-oxadiazole (3.5 mL, 26.60 mmol) was added and the mixture was stirred at 80 C. for 2 h. After the completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated to dryness. The residue was triturated with petroleum ether (40 mL) to obtain solid compound which was filtered and dried to afford 4.1 g (89.13%) of ethyl 7-bromo-1-[(5-methyl-1,2,4-oxadiazol-3-yl)methyl]-4-oxo-1,4-dihydroquinoline-3-carboxylate as pale brown solid.1H NMR (400 MHz, DMSO-d6): delta 1.29 (t, 3H), 2.50 (s, 3H), 4.22-4.27 (q, 2H), 5.89 (s, 2H), 7.63-7.65 (m, 1H), 7.97 (d, 1H), 8.12-8.14 (d, 1H), 8.85 (s, 1H).LC-MS: m/z 392.1 (M+H).

References: [1]Patent: US2010/317624,2010,A1 .Location in patent: Page/Page column 61.

12
[ 6974-32-9 ]
[ 208580-23-8 ]
[ 224175-69-3 ]

References: [1]Tetrahedron,2011,vol. 67,p. 7336 - 7342.

13
[ 208580-23-8 ]
2-(3-carboxy-1-ethyl-4-oxo-1,4-dihydroquinolin-7-yl)-5,10,15,20-tetraphenylporphyrin [ No CAS ]

References: [1]Tetrahedron,2011,vol. 67,p. 7336 - 7342.

14
[ 208580-23-8 ]
C₅₆H₃₇N₅O₃Zn [ No CAS ]

References: [1]Tetrahedron,2011,vol. 67,p. 7336 - 7342.

15
[ 87-13-8 ]
[ 591-19-5 ]
[ 208580-23-8 ]

Yield	Reaction Conditions	Operation in experiment
30%	In ethanol;Reflux;	j00380j 3-Bromoaniline (10 g, 58.13 mmol) and diethyl 2-(ethoxymethylene)malonate (12.57 g, 58.13 mmol) were suspended in ethanol (60 mL), and the reaction mixture was heatedto reflux overnight. Then, the crude mixture was concentrated, and the resulting residue was re-suspended in diphenyl ether. Next, the suspension was heated to 250 C for 90 minutes. The mixture was then cooled to about 35 - 40 C and filtered through a sintered glass funnel. The isolated solid was washed with 2:1 ethyl acetate:hexanes, and recrystallized from 70% ethanol affording ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate as a white solid(5.11 g, 30%).
30%	In ethanol; at 250℃;	3-Bromoaniline (10 g, 58.13 mmol) and diethyl 2-(ethoxymethylene)malonate (12.57 g, 58.13 mmol) were suspended in ethanol (60 mL), and the reaction mixture was heated to reflux overnight. Then, the crude mixture was concentrated, and the resulting residue was re-suspended in diphenyl ether. Next, the suspension was heated to 250 C for 90 minutes. The mixture was then cooled to about 35- 40 C and filtered through a sintered glass funnel. The isolated solid was washed with 2:1 ethyl acetate:hexanes, and recrystallized from 70% ethanol affording ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate as a white solid (5.11 g, 30%).

References: [1]Patent: WO2015/131035,2015,A1 .Location in patent: Paragraph 00380.
[2]Patent: WO2015/171610,2015,A2 .Location in patent: Paragraph 000356.
[3]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 74 - 78.
[4]Patent: WO2009/147433,2009,A1 .
[5]Photochemical and Photobiological Sciences,2019,vol. 18,p. 1910 - 1922.
[6],2020,vol. 10,p. 7523 - 7540.

16
[ 74-88-4 ]
[ 208580-23-8 ]
ethyl 7-bromo-1-methyl-4-oxo-1,4-dihydroquinoline-3-carboxylate [ No CAS ]