[ CAS No. 13924-94-2 ]

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2D
Chemical Structure| 13924-94-2
Chemical Structure| 13924-94-2
Structure of 13924-94-2

Quality Control of [ 13924-94-2 ]

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Product Details of [ 13924-94-2 ]

CAS No. :13924-94-2MDL No. :MFCD09753440
Formula :C6H7N3O2Boiling Point :363°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :153.14Pubchem ID :14536427
Synonyms :

Computed Properties of [ 13924-94-2 ]

TPSA : 78.1 H-Bond Acceptor Count : 5
XLogP3 : - H-Bond Donor Count : 1
SP3 : 0.17 Rotatable Bond Count : 2

Safety of [ 13924-94-2 ]

Signal Word:WarningClassN/A
Precautionary Statements:P261-P280-P305 P351 P338UN#:N/A
Hazard Statements:H302-H315-H319-H332-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 13924-94-2 ]

  • Upstream synthesis route of [ 13924-94-2 ]
  • Downstream synthetic route of [ 13924-94-2 ]

[ 13924-94-2 ] Synthesis Path-Upstream   1~3

  • 1
  • [ 33332-25-1 ]
  • [ 13924-94-2 ]
YieldReaction ConditionsOperation in experiment
39.5%
Stage #1: With sodium azide; triphenylphosphine In dimethyl sulfoxide at 120℃; for 4.00 h;
Stage #2: With hydrogenchloride In water; dimethyl sulfoxide at 120℃; for 2.00 h;
Methyl 5-(chloropyrazine)-2-carboxylate (36 7) (2g, 0.0115mmol) was dissolved in 80mL of 87 DMSO. 88 Sodium azide (3g, 0.0463mmol) and 39 triphenylphosphene (4.6g, 0.1738mmol) were added and the mixture was refluxed at 120°C for 4h. 20mL of 1N 89 HCl was added and the reaction was continued at 120°C for 2h. The mixture was cooled and neutralized by using 90 aqueous NaHCO3 solution and 91 product was extracted in ethyl acetate, dried using Na2SO4. The ethyl acetate fraction was evaporated and washed with n-pentane to get 0.7g (yield 39.5percent) yellow solid of compound 8. 1H NMR (400MHz, DMSO‑d6) δ 8.53 (d, J=1.2Hz, 1H), 7.91 (d, J=1.2Hz, 1H), 7.39 (s, 2H), 3.79 (s, 3H). C6H7N3O2 [M]: 153.14; MS (ESI) m/z: [M-H]+: 152.05.
Reference: [1] European Journal of Pharmaceutical Sciences, 2018, vol. 124, p. 165 - 181
[2] Tetrahedron Letters, 2013, vol. 54, # 5, p. 414 - 418
[3] ACS Medicinal Chemistry Letters, 2013, vol. 4, # 4, p. 414 - 418
  • 2
  • [ 1204527-84-3 ]
  • [ 13924-94-2 ]
YieldReaction ConditionsOperation in experiment
78%
Stage #1: at 60℃; for 1.00 h;
Stage #2: at 20℃;
To a solution of Int-1 (100 g, 1.063 mmol)) in DME (400 mL) was added Int-2 (155 g, 1.595 mmol) at room temperature. The reaction mixture was heated to 85° C. and stirring was continued overnight. The volatiles were concentrated under reduced pressure, then residue was diluted with water (500 mL) and dichloromethane (500 mL). The pH was adjusted to neutral by using sat. NaHCO3. The organic layer was separated, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified through silica gel column chromatography, eluted with ethyl acetate to afford Int-3 (40 g, 28.5percent) as syrup. To a solution of Int-3 (40 g, 0.303 mol) in acetonitrile (200 mL) was added N-Iodo succinamide (81 g, 0.3636 mol) at room temperature, and then stirred for 1 hour. The reaction mixture was poured into water and stirred for 30 minutes. The precipitated solids were filtered and solids were triturated in ethyl acetate (1 L), filtered solid, and washed with ethyl acetate. Then filtrate was washed with 10percent Na2CO3 solution (250 mL), water, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford Int-4 (18.1 g, 23percent) as a solid. Mass (m/z): 259 [M++1]. 1H NMR (200 MHz, dmso-d6): δ 8.43 (d, J=8 Hz, 1H), 7.69-7.53 (m, 2H), 7.23 (t, J=6.6 Hz, 1H), 2.42 (s, 3H). To a suspended solution of Int-5 (12 g, 46.51 mmol) in IPA: water (80 mL: 30 mL) was added Pd Cl2(dppf).DCM (7.5 g, 9.3 mmol), tertiary butyl amine (4.9 g, 69.76 mmol) and Na2CO3 (7.3 g, 69.76 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirring was continued overnight. The reaction mixture was allowed to room temperature, and then diluted with dichloromethane (250 mL) and water. The organic layer was separated, washed with 10percent Na2CO3 solution (75 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified through silica gel column chromatography, eluted product with ethyl acetate to afford Int-6 (4.8 g, 42.4percent) as a solid. Mass (m/z): 244 [M++1]. 1H NMR (200 MHz, dmso-d6): δ 8.51 (t, J=5 Hz, 2H), 7.71 (s, 1H0, 7.63-7.55 (m, 2H), 7.34 (t, J=7 Hz, 1H), 6.94 (t, J=7 Hz, 1H), 2.43 (s, 3H). To a solution of Int-7 (1 g, 5.797 mmol) in THF (10 mL) was added 4-methoxy benzyl amine (1.98 g, 14.49 mmol) at room temperature and, then stirred overnight. The reaction mixture was filtered, concentrated under reduced pressure. The residue was purified through silica gel column chromatography, eluted product with 50percent ethyl acetate/dichloromethane to afford Int-8 (800 mg, 50.6percent) as a solid. Mass (m/z): 274 [M++1]. 1H NMR (200 MHz, dmso-d6): δ 8.6 (s, 1H), 8.61-8.42 (brs, 1H), 8.01 (s, 1H), 7.23 (d, J=8.5 Hz, 2H), 6.83 (d, J=8.4 Hz, 2H). To a solution of Int-8 (800 mg, 2.925 mmol) in trifluoro acetic acid (5 mL) was stirred for 1 hour at 60° C. The reaction mixture was allowed to room temperature, and then quenched with solid sodium bicarbonate. The reaction mixture was diluted with ethyl acetate and water. The organic layer was separated, dried over anhydrous Na2SO4 and concentrated under reduced pressure rotavapour to afford Int-9 (350 mg, 78percent) as a solid. Mass (m/z): 154 [M++1]. 1H NMR (200 MHz, dmso-d6): δ 8.51 (s, 1H), 8.7.83 (s, 1H), 7.39 (brs, 2H), 3.79 (s, 3H). To a solution of Int-6 (1.58 g, 6.535 mmol) in 1,4-dioxane (25 mL) was added palladium acetate (238 mg, 1.045 mmol), Xantpos (498 mg, 1.045 mmol), Int-9 (1 g, 6.535 mmol) and cesium carbonate (3.21 g, 9.802 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirring was continued for 18 hours. The reaction mixture was concentrated under reduced pressure, then residue was diluted with ethyl acetate. The precipitated solids were filtered, then washed with water (25 mL) and dried under vacuum. The solids were purified through silica gel column chromatography, eluted product with 3percent methanol/dichloromethane to afford Int-10 (200 mg, 8.5percent) as a solid. Mass (m/z): 361 [M++1]. 1H NMR (200 MHz, dmso-d6): δ 10.8 (brs, 1H), 9.06 (s, 1H), 8.09 (s, 1H), 8.59-8.4 (m, 2H), 8.01 (s, 1H), 7.6 (d, J=7.4 Hz, 1H), 7.7.29-7.2 (m, 2H), 6.98 (t, J=7 Hz, 1H), 3.81 (s, 3H). To a solution of Int-10 (200 mg, 0.555 mmol) in methanol (4 mL) and dichloromethane (10 mL) was added hydroxyl amine solution (aqueous 50percent) (4 mL) and reaction mixture was stirred for 20 minutes at 0° C. Then sodium hydroxide solution (3 mL) was added and the reaction mixture was allowed to room temperature, then stirred for 5 hours. The volatiles were concentrated under reduced pressure, then adjusted pH to neutral by using 1N HCl at 0° C. The precipitated solids were filtered, washed with water, dichloromethane and hexanes to afford the title compound (150 mg, 75percent) as a solid. Mass (m/z): 362 [M++1]. (1H NMR 200 MHz (dmso-d6): δ 10.96 (brs, 1H), 9.01 (s, 1H), 8.72 (s, 1H), 8.54 (d, J=6.6 Hz, 1H), 8.47 (d, J=5.4 Hz, 1H), 7.99 (s, 1H), 7.6 (d, J=8.8 Hz, 1H), 7.33 (t, J=7.6 Hz, 1H), 7.24 (d, J=3.8 Hz, 1H), 6.99 (t, J=7 Hz, 1H), 6.42 (s, 1H), 2.5 (s, 3H).
Reference: [1] Patent: US2010/29638, 2010, A1. Location in patent: Page/Page column 124-125
  • 3
  • [ 67-56-1 ]
  • [ 113305-94-5 ]
  • [ 13924-94-2 ]
YieldReaction ConditionsOperation in experiment
49%
Stage #1: for 2.00 h; Reflux
Stage #2: With water; sodium hydrogencarbonate In methanol; ethyl acetate
Reflux a solution of 2.24 g (18.65 mmol) of 5-aminopyrazine-2-carbonitrile and 9.45 mL (74.40 mmol) of boron trifluoride etherate in 50 mL of methanol for 2 h.
Concentrate the reaction mixture under reduced pressure and take up the residue obtained in 200 mL of EtOAc and 10 mL of a saturated aqueous solution of NaHCO3.
Dry the organic phase over Na2SO4 and concentrate under reduced pressure.
Purify the residue obtained by silica gel column chromatography, eluding with a cyclohexane/EtOAc 1:1 mixture.
After concentration under reduced pressure, we obtain 1.4 g of methyl 5-aminopyrazine-2-carboxylate in the form of oil.
Yield=49percent
Reference: [1] Patent: US2009/318473, 2009, A1. Location in patent: Page/Page column 27
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