CAS No. :	625-92-3
Formula :	C₅H₃Br₂N
M.W :	236.89
SMILES Code :	BrC1=CN=CC(Br)=C1
MDL No. :	MFCD00014634
InChI Key :	SOSPMXMEOFGPIM-UHFFFAOYSA-N
Pubchem ID :	69369

Safety of 3,5-Dibromopyridine

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H315-H319-H335
Precautionary Statements:	P261-P305+P351+P338

Application In Synthesis of 3,5-Dibromopyridine

* 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 [ 625-92-3 ]
Downstream synthetic route of [ 625-92-3 ]

[ 625-92-3 ] Synthesis Path-Upstream 1~5

1
[ 625-92-3 ]
[ 191104-26-4 ]

References: [1] Patent: US2002/193596, 2002, A1, .

2
[ 625-92-3 ]
[ 3543-02-0 ]

References: [1] Monatshefte fuer Chemie, 1885, vol. 6, p. 664.
[2] Monatshefte fuer Chemie, 1885, vol. 6, p. 664.

3
[ 625-92-3 ]
[ 4318-78-9 ]

References: [1] Journal of Organic Chemistry, 2012, vol. 77, # 15, p. 6653 - 6656.
[2] Recueil des Travaux Chimiques des Pays-Bas, 1955, vol. 74, p. 1062,1068.
[3] Chemische Berichte, 1936, vol. 69, p. 1534,1536.
[4] Recueil des Travaux Chimiques des Pays-Bas, 1936, vol. 55, p. 122,126.
[5] Patent: CH174873, 1933, , .
[6] Chemistry - A European Journal, 2000, vol. 6, # 15, p. 2830 - 2846.

4
[ 625-92-3 ]
[ 7758-99-8 ]
[ 4318-78-9 ]

References: [1] Recueil des Travaux Chimiques des Pays-Bas, 1936, vol. 55, p. 122,126.
[2] Chemische Berichte, 1936, vol. 69, p. 1534,1536.

5
[ 625-92-3 ]
[ 952059-69-7 ]

References: [1] Patent: US2014/336182, 2014, A1, .
[2] Patent: WO2008/124083, 2008, A2, .

[ 625-92-3 ] Synthesis Path-Downstream 1~27

1
[ 625-92-3 ]
[ 124-41-4 ]
[ 18677-48-0 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1955,vol. 74,p. 1171,1174.

2
[ 625-92-3 ]
[ 4318-78-9 ]

References: [1]Journal of Organic Chemistry,2012,vol. 77,p. 6653 - 6656.
[2]Recueil des Travaux Chimiques des Pays-Bas,1955,vol. 74,p. 1062,1068.
[3]Chemistry - A European Journal,2000,vol. 6,p. 2830 - 2846.

3
[ 625-92-3 ]
[ 75806-85-8 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1932,vol. 51,p. 940,949.

4
[ 625-92-3 ]
[ 75806-85-8 ]
[ 2766-64-5 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1932,vol. 51,p. 940,949.

5
[ 13534-90-2 ]
[ 96-22-0 ]
[ 626-55-1 ]
[ 625-92-3 ]
[ 1120-87-2 ]
[ 107399-34-8 ]

References: [1]Tetrahedron,1986,vol. 42,p. 2253 - 2262.

6
[ 13534-90-2 ]
[ 626-55-1 ]
[ 625-92-3 ]
[ 1120-87-2 ]

References: [1]Tetrahedron,1986,vol. 42,p. 2253 - 2262.

7
[ 625-92-3 ]
ammonium hydroxide [ No CAS ]
[ 7758-99-8 ]
[ 4318-78-9 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1936,vol. 55,p. 122,126.
[2]Chemische Berichte,1936,vol. 69,p. 1534,1536.

8
[ 625-92-3 ]
[ 7726-95-6 ]
[ 75806-85-8 ]
[ 2766-64-5 ]

References: [1]Recueil des Travaux Chimiques des Pays-Bas,1932,vol. 51,p. 386,949.

9
[ 625-92-3 ]
[ 53710-18-2 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; potassium iodide; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 110℃; for 16h;Inert atmosphere;	A mixture of 3,5-dibromo-pyridine (20 g, 84 mmol), CuT (4.76 g, 25 mmol), KI (83.7 g,504 mmol) and N,N-dimethyl-ethane-1,2-diamine (4.4 g, 50.4 mmol) in dioxane (400 mL)was stilTed at 110C for 16 hours. The reaction solution was filtered and the filtrate wasconcentrated under reduced pressure to give a crude solid which was washed with EtOAc(100 mL) and DCM (100 mL) to give the title product as a white solid (13 g, 47%). MS:331.5 (M+H). It was used directly in the next step without further purification.
	With copper(l) iodide; potassium iodide; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 110℃; for 16h;Inert atmosphere;	A mixture of 3,5-dibromopyridine (20 g, 84 mmol), CuT (4.76 g, 25 mmol), KI (83.7 g,504 mmol) and N?, N2-dimethylethane-1,2-diamine (4.4 g, 50.4 mmol) in dioxane (400 mL) was stirred at 110C for 16 hours. During this time, the reaction progress was monitored by LC/MS. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to afford a solid, which was then washed with EtOAc (100 mL)and DCM (100 mL) to give the crude title compound as a gray solid (13 g, 47%). MS:331.50 (M+Hj. It was used in the next step without further purification.
	With copper(l) iodide; potassium iodide; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 110℃; for 16h;Inert atmosphere;	A mixture of 3,5-dibromopyridine (20 g, 84 mmol), CuT (4.76 g, 25 mmol), KI (83.7 g,504 mmol) and N?, N2-dimethylethane-1,2-diamine (4.4 g, 50.4 mmol) in dioxane (400mL) was stirred at 110C for 16 hours. During this time, the reaction progress wasmonitored by LC/MS. The reaction mixture was filtered and the filtrate was concentratedunder reduced pressure to afford a solid, which was then washed with EtOAc (100 mL) and DCM (100 mL) to give the crude title compound as a gray solid (13 g, 47%). MS:331.50 (M+Hj. It was used in the next step without further purification.

References: [1]Organic Letters,2017,vol. 19,p. 3974 - 3977.
[2]Chemistry - A European Journal,2013,vol. 19,p. 2450 - 2456.
[3]Chemistry - A European Journal,2010,vol. 16,p. 12425 - 12433.
[4]Journal of the American Chemical Society,2004,vol. 126,p. 6135 - 6149.
[5]Journal of the American Chemical Society,2007,vol. 129,p. 3054 - 3055.
[6]Heterocycles,2013,vol. 87,p. 55 - 63.
[7]Crystal Growth and Design,2012,vol. 12,p. 205 - 216.
[8]Patent: WO2014/191336,2014,A1 .Location in patent: Page/Page column 54; 55.
[9]Patent: WO2014/191340,2014,A1 .Location in patent: Page/Page column 42.
[10]Patent: WO2014/191338,2014,A1 .Location in patent: Page/Page column 43.

10
[ 625-92-3 ]
[ 870234-98-3 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 2789 - 2794.

11
[ 625-92-3 ]
[ 224311-51-7 ]
[ 57260-71-6 ]
[ 412348-60-8 ]

Yield	Reaction Conditions	Operation in experiment
20%	tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; ethyl acetate;	Example 123A 4-(5-Bromo-pyridin-3-yl)-piperazine-1-carboxylic Acid Tert-Butyl Ester A solution of the 3,5-dibromo-pyridine (12.8 g, 68.8 mmol) and piperazine-1-carboxylic acid tert butyl ester (10 g, 42.4 mmol) in 200 mL of dioxane was treated with Pd2(dba)3 (5 g, 5.5 mmol), 2-(di-tbutyl-phosphino)biphenyl (4 g, 13.4 mmol), and sodium t-butoxide (7.2 g, 75 mmol). The reaction was heated to 95° C. for 8 h then cooled and filtered through celite. The mixture was evaporated and the residue was purified by flash column chromatography on silica gel, eluding with a solvent gradient of 1:4 ethyl acetate/hexane to 100percent ethyl acetate. Recovered 2.9 g of product (20percent). MS (ESI) m/z 344 (M+H)+.

References: [1]Patent: US2003/187026,2003,A1 .

12
[ 625-92-3 ]
aqueous sodium metabisulfite [ No CAS ]
[ 624-92-0 ]
[ 445491-71-4 ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium; oxone; In tetrahydrofuran; methanol; diethyl ether; ethyl acetate;	Step 2 3-Bromo-5-Methylsulfonylpyridine To 3,5-dibromopyridine (2.96 g, 12.5 mmol) in diethyl ether (70 ml) at -78 C. was added n-butyllithium 1.6M in hexanes (8.6 ml, 13.7 mmol) and the resulting mixture was stirred in the cold for 3 hours. Dimethyl disulfide (1.12 ml, 12.5 mmol) was added and the mixture was warmed to room temperature, then partitioned between ether and water. To the crude product from evaporation of the organic phase was added tetrahydrofuran (80 ml), methanol (20 ml), oxone (17 g) and enough saturated aqueous sodium bicarbonate to afford a slightly basic medium. After stirring for 4 hours at room temperature, an excess of 1M aqueous sodium metabisulfite was added, the organic solvents were evaporated, and the residue was partitioned between ethyl acetate and water. The crude product from the organic phase was stirred in a small volume of ethyl acetate and filtered to afford the 3-Bromo-5-methylsulfonylpyridine compound as a solid.

References: [1]Patent: US2003/96829,2003,A1 .

13
[ 625-92-3 ]
[ 29608-05-7 ]
[ 1044920-96-8 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; In toluene; at 120℃;	EXAMPLE 21 Preparation of (5-Bromopyridin-3-yl)-4-piperidin-1-ylmethylphenyl)amine (73). A vial was charged with palladium acetate (16.8 mg, 5 mol %), (+/-)BINAP (46.7 mg, 5 mol %) and toluene (5 mL). The mixture was stirred and flushed with nitrogen for 10 min. Another round bottom flask was charged with 3,5-dibromopyridine (355.4 mg, 1.5 mmol), amine 72 (342.5 mg, 1.8 mmol) and cesium carbonate (2.44 g, 7.5 mmol). Then the Pd(OAc)2/BINAP solution was added to the flask and the vial was rinsed with additional toluene (5 mL). The resulting mixture was flushed with nitrogen for 5 min and subsequently heated in a preheated oil bath at 120 C. under vigorous stirring overnight. After cooling, the mixture was filtered and the solid was washed with CH2Cl2. The organic layers were combined and evaporated under reduced pressure to give a brown solid. The solid was purified via flash column chromatography, eluding with hexane/EtOAc to give the product as a yellow oil.

References: [1]Patent: US2007/32475,2007,A1 .Location in patent: Page/Page column 41.

14
[ 625-92-3 ]
[ 73183-34-3 ]
[ 1012085-50-5 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;palladium diacetate; In tetrahydrofuran; for 5h;Reflux; Inert atmosphere;Product distribution / selectivity;	Example 3; Synthesis of Compound of Formula IV To a flame dried 3-neck round bottom flask fitted with a condenser, a nitrogen inlet, and a rubber septum was added PcyBiPh (84 mg, 0.20 mmol) and Pd(OAc)2 (19.0 mg, 0.080 mmol). The flask was then protected from the atmosphere and was charged with anhydrous THF (10 mL) and the solution was degassed by purging N2 through the stirred solution. After 15 minutes, the reaction mixture was charged with 3,5-dibromopyridine (0.315 g, 1.33 mmol), pinacolate diborane (0.338 g, 2.66 mmol), dry KOAc (0.217 g, 12.2 mmol), and the mixture was heated at reflux for 5 hours. The reaction mixture was cooled to room temperature and charged with the compound 2, (1.60 g, 3.2 mmol), Na2CO3 (1.20 g, 11.3 mmol), Cs2CO3 (1.10 g, 3.38 mmol), and degassed H2O (0.25 mL). The mixture was then heated at reflux for 20 hours, after which it was cooled to room temperature and concentrated to dryness. The crude material thus obtained was suspended in H2O, collected by filtration, and washed with H2O. The dried solid was chromatographed through SiO2 (3-5% MeOH/CH2Cl2) to give compound of formula IV as a colorless solid. Yield: 0.851 g, 64%. 1H NMR (400 MHz, CD3OD/CD2Cl2, 25 C.) delta7.46 (m, 4H), 7.66 (t, 4H), 7.72 (m, 6H), 7.83 (m, 2H), 7.90 (m, 2H), 8.07 (m, 10H), 8.26 (m, 4H), 8.33 (t, 1H), 8.44 (t, 4H), 8.54 (m, 4H), 8.89 (m, 4H), 8.93 (m, 2H).
	With potassium acetate;palladium diacetate; CyJohnPhos; In tetrahydrofuran; for 5h;Inert atmosphere; Reflux;	EXAMPLE 3: synthesis of compound of formula IV[0040] To a flame dried 3-neck round bottom flask fitted with a condenser, a nitrogen inlet, and a rubber septum was added PcyBiPh (84 ing, 0.20 mmol) and Pd(OAc)2 (19.0 mg, 0.080 mmol). The flask was then protected from the atmosphere and was charged with anhydrous THF (10 mL) and the solution was degassed by- purging N2 through the stirred solution. After 15 minutes,, the reaction mixture was charged with 3.5-dibromopyridine (0.315 g, 1.33 mmol), pinacolate diborane (0.338 g, 2.66 mmol), dry KOAc (0.217 g, 12.2 mmol), and the mixture was heated at refiux for 5 hours. The reaction mixture was cooled to room temperature and charged with the compound 2, (1.60 g, 3.2 mmol), Na3CO3 (1.20 g, 11.3 mmolX Cs2CO3 (1.10 g, 3.38 mmol). and degassed H2O (0.25 mL). The mixture was then heated at refiux for 20 hours, after which it was cooled to room temperature and concentrated to dryness. The crude materia. thus obtained was suspended in H2O. collected by filtration, and washed with H2O. The dried solid was chromatographed through Sitheta2 (3-5% MeOH/CH2Cl2) to give compound of formula IV as a colorless solid. Yield: 0.851 g, 64%. 1H NMR (400 MH/, CD3OD/CD2Cl2, 25 C) 61.46 Cm, 4H), 7.66 (t, 4H), 7.72 (m, 6H), 7.83 (m, 2H), 7.90 (m, 2H), 8.07 (m, 10H), 8.26 (m, 4H), 8.33 (t, 1H), 8.44 (t, 4H), 8.54 (n% 4H), 8.89 (m, 4H), 8.93 (m, 2H).
	With potassium acetate;palladium diacetate; CyJohnPhos; In 1,4-dioxane; at 110℃; for 3h;Inert atmosphere;	EXAMPLE 9: synthesis of compound of formula XJ0047J To a schlenk tube was charged 3,5-dibromopyridine (50 mg, 0.21 mmol), pinacolate diborane (0.117 g, 0.462 mmol), dry KOAc (0.1 g, 1 mmol), ligandPCvBin (6.7 mgt 0.0 3 mg, 0.03 mmoL 3%). The schlenk tube was evacuated and filled with argon three times. The schlenk was placed in an argon atmosphere. Anhydrous dioxane (6 tnL) was added. The flask was then heated at 1 K) C for 3 hours under argon atmosphere. Then compound 3 (0.25 g, 0.5 mmol), dry KOAc (0,1 g, 1 mmolX, ligand PCyBin (6.7 mg, 0,017 mmol, 4%) and Pd(OAc)Z (3 nig, 0.013 mmol, 3%) and 5 ml dioxane were added into above reaction solution, then reiluxed at 1 10 X overnight under argon atmosphere. Then cooled to ambient temperature. Distilled water (30 mL) was added via a funnel, and the resulting mixture was filtered on a Bchner funnel. The filtrate was transferred to a separatory funnel and extracted with CIhCh O x 30 mL). The combined organic phases were dried over Na^SO4, filtered on filter paper and concentrated to dryness by rotary evaporation (30 C, 25 mmHg). The resulting yellow solid was purified by column chromatography affording as a white solid 94 mg (45%). 1H NMR (400 MHz, CDCI3) delta 8.94 (m, 6H), 8.64 (m, 4H), 8.20 (m, 1H), 7.97-7.91 (m, 16H). 7.82-7.63 (m, 18H), 7.41 (m, 4H).

References: [1]Journal of Natural Products,2017,vol. 80,p. 1205 - 1209.
[2]Patent: US2010/174086,2010,A1 .Location in patent: Page/Page column 10-11.
[3]Patent: WO2010/80471,2010,A1 .Location in patent: Page/Page column 19.
[4]Patent: WO2010/80471,2010,A1 .Location in patent: Page/Page column 23-24.

15
[ 625-92-3 ]
[ 233770-01-9 ]
[ 53710-18-2 ]

References: [1]Chemistry - A European Journal,2010,vol. 16,p. 12425 - 12433.

16
[ 625-92-3 ]
[ 870119-58-7 ]
[ 1013405-25-8 ]

References: [1]Chemistry of Materials,2011,vol. 23,p. 274 - 284.

17
[ 625-92-3 ]
[ 214360-60-8 ]
[ 1351665-26-3 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 5206 - 5209.

18
[ 625-92-3 ]
[ 1082549-89-0 ]
[ 1082549-91-4 ]

Yield	Reaction Conditions	Operation in experiment
64.4%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; toluene; for 9h;Reflux;	Step 5: Synthesis of Intermediate (G)45.1 g (84 mmol) of the intermediate (F), 20.0 g (84 mmol) of 3,5-dibromopyridine, and 2.44 g (2.1 mmol) of tetrakis-(triphenyl phosphine) palladium were suspended in 600 ml of tetrahydrofuran and 400 ml of toluene, and then the suspension was added with a solution in which 23.3 g (169 mmol) of potassium carbonate was dissolved in 400 ml of water. The obtained mixture was heated and refluxed for 9 hours. The reaction fluid was separated into two layers, and an organic layer thereof was cleaned with a sodium chloride saturated aqueous solution and dried with anhydrous sodium sulfate.The organic solvent was removed by distillation under a reduced pressure, and the residue was recrystallized by toluene. The precipitated crystals were separated by filtration and cleansed with toluene to provide 30.7 g (64.4%) of the intermediate (G).

References: [1]Patent: US2012/280221,2012,A1 .Location in patent: Page/Page column 23; 25.

19
[ 625-92-3 ]
[ 197223-39-5 ]
[ 1443358-65-3 ]

References: [1]Tetrahedron Letters,2013,vol. 54,p. 3658 - 3661.
[2]Chemical Communications,2015,vol. 51,p. 12419 - 12422.

20
[ 625-92-3 ]
[ 5400-79-3 ]
ethyl 3-(5-bromopyridin-3-yl)-3-hydroxycyclopentanecarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Step 1 : A solution of THF:toluene (2.1 1 mL:2.11 mL) and -BuLi (0.923 ml, 1.48 mmol) was cooled to -10 C. The reaction mixture was purged/filled with argon (3x). w-Butyl magnesium chloride (0.369 ml, 0.739 mmol) was added to the reaction mixture and stirred for 30 minutes. 3,5-Dibromopyridine (0.5 g, 2.1 11 mmol) was added to the reaction mixture over the course of 30 minutes, keeping bath below -10 C and stirred for 1 hour. Ethyl 3- oxocyclopentanecarboxylate (0.330 g, 2.11 1 mmol) was added to the reaction mixture and stirred at -10 C for ~5 minutes. The reaction mixture was warmed to room temperature, diluted with saturated ammonium, extracted DCM (3x), and combined organic layers were concentrated under reduced pressure. The residue was purified by silica gel chromatography (ethyl acetate/hexanes) to afford ethyl 3-(5-bromopyridin-3-yl)-3-hydroxycyclopentanecarboxylate. MS ESI calc'd for Ci3Hi7BrN03 [M + H]+ 314 and 316, found 314 and 316.

References: [1]Patent: WO2013/192098,2013,A1 .Location in patent: Paragraph 00274.

21
[ 22929-52-8 ]
[ 625-92-3 ]
3-(5-bromo-pyridin-3-yl)-tetrahydro-furan-3-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
125 mg		To a cooled (?15° C.) solution of 3,5-dibromopyridine (1.2 g, 5.0 mmol) in THF (12 mL) is added a solution of isopropylmagnesium chloride-lithium chloride complex in THF (1.7 M; 2.9 mL, 4.9 mmol). The resultant mixture is stirred at ?15° C. for 30 min and dihydro-furan-3-one (517 mg, 6.0 mmol) is added. After stirring for 16 h, the reaction is quenched with saturated aqueous NH4Cl solution and is extracted with EtOAc. The combined organic extracts are washed with water and brine, dried and concentrated under reduced pressure. Purification by flash column chromatography provides 125 mg of 3-(5-bromo-pyridin-3-yl)-tetrahydro-furan-3-ol.

References: [1]Patent: US2014/323468,2014,A1 .Location in patent: Paragraph 0588.

22
[ 625-92-3 ]
[ 320-72-9 ]
C₅H₃Br₂N*C₇H₄Cl₂O₃ [ No CAS ]

References: [1]Chemistry - A European Journal,2017,vol. 23,p. 4936 - 4943.

23
[ 625-92-3 ]
[ 581060-27-7 ]
C₁₆H₂₃BrN₂O₂S [ No CAS ]

References: [1]Patent: US2017/283397,2017,A1 .Location in patent: Paragraph 0117.

24
[ 109-11-5 ]
[ 625-92-3 ]
4-(5 -bromopyridin-3-yl)morpholin-3-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane; at 100℃; for 12h;Inert atmosphere;	A solution of Pd2(dba)3 (322 mg, 0.352 mmol) and XantPhos (204 mg, 0.352 mmol) in dioxane (10 mL) was stirred at 50 C for 5 min under N2. Then 3,5-dibromopyridine (1.00 g, 4.20 mmol), <strong>[109-11-5]morpholin-3-one</strong> (356 mg, 0.352 mmol) and Cs2C03 (2.30 g, 7.00 mmol) was added to the solution. The resulting mixture was stirred at 100 C for 12 h under N2. A black brown solid was formed. TLC (EtO Ac/PE = 2: 1) showed starting material was consumed completely and the new point was formed at Rf = 0.28. The reaction mixture was filtered and the filtrate was concentrated. Amounts of crude product were increased using the same procedure. The combined amounts of crude were then purified by combi flash (with 6% EtOAc in pentane) to give 4-(5-bromopyridin-3-yl)<strong>[109-11-5]morpholin-3-one</strong> (510 mg, yield: 51%) as a yellow solid. NMR (400 MHz, CDCb) d 3.81 (2H, t , J = 5.2 Hz), 4.05 (2H, t, J= 5.2 Hz), 4.36 (2H, s), 7.97 (1H, d, J = 2.0 Hz), 8.57 (2H, dd, J = 4.0, 2.0 Hz).

References: [1]Patent: WO2019/126730,2019,A1 .Location in patent: Paragraph 0458.

25
[ 625-92-3 ]
[ 67104-97-6 ]
2-(5-bromopyridin-3-yl)-5-methyl-1,2,5-thiadiazolidine 1,1-dioxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 100℃; for 16h;Inert atmosphere;	Step 4: Preparation of 2-(5-bromopyridin-3-yl)-5-methyl-1,2,5-thiadiazolidine 1,1-dioxide. [0771] A mixture of <strong>[67104-97-6]2-methyl-1,2,5-thiadiazolidine 1,1-dioxide</strong> (50 mg, 0.37 mmol), 3, 5- dibromopyridine (261 mg, 1.10 mmol), Cul (21 mg, 0.11 mmol), CS2CO3 (179 mg, 0.550 mmol) and DMEDA (19 mg, 0.22 mmol) in anhydrous dioxane (4 mL) was degassed and purged with N2 for 3 times. Then the resulting reaction mixture was heated at 100 C for 16 hours under N2 atmosphere. The reaction mixture turned into blue suspension from yellow. LCMS showed the purity of the desired product is 31% (Rt = 0.692 min; MS Calcd: 291.0; MS Found: 291.6 [M+H]+). The reaction mixture was filtered and the filtrate was concentrated. The residue was purified by Combi Flash (20% to 60% EtOAc in PE) to give 2-(5- bromopyridin-3-yl)-5-methyl-1,2,5-thiadiazolidine 1,1-dioxide (58 mg, yield: 54%) as a white solid. NMR (400 MHz, CDCb) d 2.88 (3H, s), 3.53-3.58 (2H, m), 3.87 (2H, t, J= 6.4 Hz), 7.81 (1H, t, J= 2.4 Hz), 8.39 (1H, d, J= 2.4 Hz), 8.46 (1H, d, J= 2.0 Hz).

References: [1]Patent: WO2019/126731,2019,A1 .Location in patent: Paragraph 0771.

26
[ 625-92-3 ]
[ 133730-34-4 ]
3,5-bis(2,4-dimethoxyphenyl)pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In 1,4-dioxane; water; at 110℃;	In a 100 ml three-necked flask, 3,5-dibromopyridine and <strong>[133730-34-4]2,4-dimethoxyphenylboronic acid</strong> were added thereto in a molar ratio of 1: 2, and then anhydrous sodium carbonate and the catalyst 10% mol of [1,1'-bis (Diphenylphosphino) ferrocene]palladium dichloride, using 1,4-dioxane and water in a volume ratio of 4: 1 as a solvent, refluxing at 110 C in an oil bath overnight, the reaction is complete The solvent was evaporated, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, and the mixture was separated through a silica gel column to obtain 3,5-bis (2,4-dimethoxyphenyl) pyridine as a white solid with a yield of 78%.
	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 110℃;	In a 100 mL three-necked flask, 2.4 g of 3, 5-dibromopyridine (CAS: 625-92-3) and 3.6 g of 2, 4-dimethoxyphenylboronic acid were added to the beaker at a molar ratio of 1: 2. Then add 2.1g of anhydrous sodium carbonate and 0.4g of tetratriphenylphosphine palladium, use 1,4-dioxane 80 mL and 20 mL of water as solvents, and heat to reflux at 110 C in an oil bath overnight. The solvent was evaporated, extracted with water and dichloromethane, dried over anhydrous sodium sulfate, and the organic phase was separated. The obtained organic phase was concentrated and purified by column chromatography to obtain bis (2,4-dimethoxyphenyl) pyridine as a white solid.

References: [1]Patent: CN110041248,2019,A .Location in patent: Paragraph 0047-0049.
[2]Patent: CN110642684,2020,A .Location in patent: Paragraph 0041; 0101; 0109; 0112; 0113.

27
[ 625-92-3 ]
[ 945865-80-5 ]
C₂₁H₁₃NO₄ [ No CAS ]

References: [1]Angewandte Chemie - International Edition,2020,vol. 59,p. 16755 - 16763.
Angew. Chem.,2020,vol. 132,p. 16898 - 16906,9.

Historical Records

Technical Information

• Alkyl Halide Occurrence • General Reactivity • Grignard Reaction • Hiyama Cross-Coupling Reaction • Kinetics of Alkyl Halides • Kumada Cross-Coupling Reaction • Preparation of Amines • Reactions of Alkyl Halides with Reducing Metals • Reactions of Amines • Reactions of Dihalides • Stille Coupling • Substitution and Elimination Reactions of Alkyl Halides • Suzuki Coupling

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Alternative Products

Product Details of 3,5-Dibromopyridine

Safety of 3,5-Dibromopyridine

Application In Synthesis of 3,5-Dibromopyridine

[ 625-92-3 ] Synthesis Path-Upstream 1~5

[ 625-92-3 ] Synthesis Path-Downstream 1~27

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