[ CAS No. 74290-65-6 ]

Name: 3-Bromo-5-methylpyrazin-2-amine
Brand: Ambeed
SKU: A215877
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COA GC NMR CNMR HPLC/UPLC LC-MS SDS

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Product Details of [ 74290-65-6 ]

CAS No. :	74290-65-6	MDL No. :	MFCD09750037
Formula :	C₅H₆BrN₃	Boiling Point :	275°C at 760 mmHg
Linear Structure Formula :	-	InChI Key :	-
M.W :	188.03	Pubchem ID :	9899043
Synonyms :

Computed Properties of [ 74290-65-6 ]

TPSA :Topological Polar Surface Area	51.8	H-Bond Acceptor Count :	3
XLogP3 :	0.9	H-Bond Donor Count :	1
SP3 :	0.20	Rotatable Bond Count :	0

Safety of [ 74290-65-6 ]

Signal Word:	Warning	Class	N/A
Precautionary Statements:	P261-P280-P305 P351 P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H332-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 74290-65-6 ]

Upstream synthesis route of [ 74290-65-6 ]
Downstream synthetic route of [ 74290-65-6 ]

[ 74290-65-6 ] Synthesis Path-Upstream 1~2

1
[ 5521-58-4 ]
[ 74290-65-6 ]

Yield	Reaction Conditions	Operation in experiment
88%	With pyridine; bromine In dichloromethane at 20℃;	To a solution of 5-methylpyrazin-2-amine (5.00g, 45.8 mmol) and pyridine (4.35g,55.0 mmol) in DCM (250 mL) was added bromine (8.80 g, 55.0 mmol). The mixture was stirredat rt overnight. To the reaction mixture was added water (150 mL), and the resulting mixture waspartitioned. The organic layer was washed with saturated brine (100 mL), dried over anhydroussodium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound asa yellow solid (7.64 g, 88 percent).MS (ESI, pos. ion) m/z: 190.2 [M+Ht;1H NMR (400 MHz, CDCh) 8 (ppm): 7.83 (s, lH), 4.93 (s, 2H), 2.41 (s, 3H).
69%	With N-Bromosuccinimide In dichloromethane at 0 - 30℃; for 1.00 h; Inert atmosphere	[00790] To a mixture of 5-methylpyrazin-2-amine (10 g, 92 mmol) in DCM (300 mL) was added BS (16 g, 91.63 mmol) in one portion at 0 °C under N2. The mixture was stirred at 30 °C for 1 hr. The resulting mixture was poured into saturated aq. Na2S03 (100 mL) and the aqueous phase was extracted with EtOAc. The combined organic layers were washed with brine, dried with Na2S04, filtered and concentrated under reduced pressure. The residue was purified by column chromatography to afford 3-bromo-5-methyl-pyrazin-2-amine (12 g, 69percent yield,) as a light yellow solid. MR (400 MHz, CDCh-d) δ ppm 7.82 (s, 1H) 4.79 - 5.03 (m, 2 H) 2.39 (s, 3 H).
65%	With N-Bromosuccinimide In dichloromethane at 0 - 20℃; for 12.00 h;	Step 1. 3-Bromo-5-methylpyrazin-2-amine. To a cooled, 0° C., solution of 5-methylpyrazin-2-amine (5.00 g, 0.05 mol) in DCM (230 mL) was added 1-bromopyrrolidine-2,5-dione (8.97 g, 0.05 mol) all at once. The reaction mixture was allowed to warm to room temperature and stirred for 12 h. The reaction was quenched with 1 N sodium thiosulfate (50 mL), the layers were separated and the organic phase was extracted with water (2*50 mL). The combined organic layers were dried (Na₂SO₄), and the solvent was removed under reduced pressure. Purification (FCC, SiO₂, 0-50percent, EtOAc/hexanes) afforded the title compound as a yellow solid (8.61 g, 65percent). [M+H]=188.9/190.11

56.4%

With pyridine; bromine In chloroform for 0.50 h;

To a suspension of 5-methylpyrazin-2-amine (1.09g, 10 mmol) in chloroform (100 mL) was added pyridine(0.85 ml., 10.5 mmol). The mixture was stirred in a foilwrappedflask fitted with an addition funnel, and a solution ofbromine (0.54 ml., 10.5 mmol) in chloroform (10 mL) wasadded dropwise over 10 min. The mixture was allowed toreact an additional 20 minutes after addition was completeand then poured into a separatory funnel containing 10 mLwater. The phases were separated and the organics washedagain with water, dried over sodium sulfate, filtered and concentratedin vacuo. The resulting red oil was purified by silicagel chromatography with 12-100percent EtOAc/hexanes. Themajor UV active peak was collected to give 3-bromo-5-methylpyrazin-2-amine (1.06 g, 5.64 mmol, 56.4percent yield) as a cream-colored solid.

Reference： [1] Patent: WO2018/108125, 2018, A1. Location in patent: Paragraph 00511
[2] Patent: WO2018/136265, 2018, A1. Location in patent: Paragraph 00790
[3] Patent: US2014/275531, 2014, A1. Location in patent: Paragraph 0353
[4] Patent: JP5714745, 2015, B2. Location in patent: Paragraph 0687; 0688
[5] Patent: US5866568, 1999, A
[6] Patent: US5668137, 1997, A

2
[ 5521-58-4 ]
[ 74290-65-6 ]
[ 74290-68-9 ]

Yield	Reaction Conditions	Operation in experiment
50%	Stage #1: With hydrogen bromide; acetic acid In chloroform at 50℃; for 0.50 h; Darkness Stage #2: With bromine In chloroform at 55℃; for 21.00 h; Stage #3: With sodium carbonate In chloroform; water	A solution of HBr/CH₃CO₂H (360 g (260 mL), 1.50 mol, 33percent HBr in CH₃CO₂H) in anhydrous CHCl₃ (300 mL) was added over 15 min to a solution of 5-methylpyrazin-2-amine 15 (42 g, 0.38 mmol) in CHCl₃ (1 L). The reaction flask was wrapped in aluminum foil and heated to 50 °C for 30 min in the dark whereupon a solution of Br₂ (68 g, 0.42 mmol) in CHCl₃ (500 mL) was added dropwise over 3 h during which time the internal temperature of the reaction never exceeded 55 °C. After 18 h at 55 °C the solvent was evaporated under reduced pressure. The crude mixture was diluted with water (200 mL) and the pH was adjusted to pH=9 by the addition of solid Na₂CO₃. The suspension was filtered under vacuum and the filtrate was extracted with EtOAc (1 L.x.5). The combined organic extracts were concentrated under reduced pressure and purified by flash silica gel chromatography eluting with petroleum ether/EtOAc (5:1-->1:1) to give compound 6-bromo-5-methylpyrazin-2-amine 17a (36 g, 50percent) as a light orange solid; mp 154-157 °C; IR (KBr): 3315, 3188, 1744, 1638, 1575, 1482, 1375, 1308, 1051 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ=7.84 (s, 1H), 4.55 (br s, 2H), 2.52 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ=152.2, 141.8, 138.4, 129.2, 22.2; HRMS-ESI: calcd for C₅H₇BrN₃ (M+H)⁺: 187.9823 and 189.9803; found: 187.9816 and 189.9796. An analytical sample of 3-bromo-5-methylpyrazin-2-amine (17b) was also isolated for spectroscopic analysis; mp 56-57 °C. ¹H NMR (400 MHz, CDCl₃): δ=7.80 (s, 1H), 4.95 (br s, 2H), 2.38 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ=150.6, 142.8, 139.9, 125.2, 19.7; HRMS-ESI: calcd for C₅H₇BrN₃ (M+H)⁺: 187.9823 and 189.9803; found: 187.9817 and 189.9796.

Reference： [1] Journal of Heterocyclic Chemistry, 1980, vol. 17, p. 143 - 147
[2] Tetrahedron, 2011, vol. 67, # 47, p. 9063 - 9066

[ 74290-65-6 ] Synthesis Path-Downstream 1~10

1
[ 74290-65-6 ]
NaCu(CN)2 [ No CAS ]
[ 17890-82-3 ]

Reference： [1]Synthesis,1990,p. 659 - 660

2
[ 74290-65-6 ]
[ 38941-47-8 ]
3-cyclohexyl-5-methyl[1,2,4]triazolo[4,3-a]pyrazin-8-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
2%	With triethylamine; In 1-methyl-pyrrolidin-2-one; at 225℃; for 3h;Sealed tube; Microwave irradiation;	Example 171 Preparation of 3-cyclohexyl-5-methyl[1,2,4]triazolo[4,3-a]pyrazin-8-amine To a reaction container for microwave were added <strong>[74290-65-6]3-bromo-5-methyl-pyrazin-2-amine</strong> (570 mg), cyclohexanecarbohydrazide (530 mg), triethylamine (625 muL), and N-methylpyrrolidone (3 mL), the container was sealed, and the resulting mixture was stirred under microwave radiation at 225 C. for 3 hours. The reaction solution was purified by silica gel column chromatography (solvent: hexane/ethyl acetate=25/75 to 0/100 to solvent: ethyl acetate/methanol=100/0 to 80/20) to give the title compound (13.9 mg) (yield 2%) as a pale yellow solid. MS(ESI) m/z: 232 [M+H]+

Reference： [1]Patent: US2019/185479,2019,A1.Location in patent: Paragraph 1493; 1494; 1495

3
[ 140-89-6 ]
[ 74290-65-6 ]
6-methyl[1,3]thiazolo[4,5-b]pyrazine-2(3H)-thione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.75 g	With hydrogenchloride; In 1-methyl-pyrrolidin-2-one; at 150℃; for 4h;	An N-methylpyrrolidone solution (10.0 mL) of <strong>[74290-65-6]2-amino-3-bromo-5-methylpyrazine</strong> (2.00 g) synthesized by the method described in and potassium ethyl xanthogenate (3.41 g) was stirred with heating at 150C for 4 h The reaction mixture was cooled to room temperature and 0.5 mol/L hydrochloric acid (20 mL) was added. The precipitated solid was collected by filtration, washed with water and dried under reduced pressure to give the title compound (1.75 g). MS(ESI)m/z; 184[M+H]+

Reference： [1]Patent: EP3372601,2018,A1.Location in patent: Paragraph 0867; 0868

4
[ 67-56-1 ]
[ 124-41-4 ]
[ 74290-65-6 ]
[ 89464-87-9 ]