1,2-Dimethoxyethane → HCID 118046691, compound

HRID 595869Notes

Reaction equation

HRID 595869 reaction equation
Br[C:2]1[N:3]=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=1.CC1(C)C(C)(C)OB([C:17]2[CH2:26][CH2:25][C:20]3([O:24][CH2:23][CH2:22][O:21]3)[CH2:19][CH:18]=2)O1.COCCOC.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.C(Cl)Cl>[O:21]1[C:20]2([CH2:25][CH2:26][C:17]([C:2]3[N:3]=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=3)=[CH:18][CH2:19]2)[O:24][CH2:23][CH2:22]1

Participants

7

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 5995392-Amino-5-bromopyrazineHCID 36970768-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro(4.5)dec-7-ene

Product 1

HCID 118046691HCID 118046691, compoundYield 57.4%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To 5-bromopyrazin-2-amine (225 mg, 1.293 mmol) was added 4,4,5,5-tetramethyl-2-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane (482 mg, 1.810 mmol), PdCl2(dppf)-CH2Cl2 adduct (84 mg, 0.103 mmol), DME (3.5 mL) and then last sodium carbonate 2M (1.616 mL, 3.23 mmol). The reaction was microwaved at 120° C. for 15 min. To the reaction was added 80 mL of DCM, washed with water (1×), dried sodium sulfate, filtered and concentrated to residue. The crude was purified by silica gel chromatography using 12 gram column (solid load) eluting with 10-90% ethyl acetate and heptane. The desired fractions were concentrated to constant mass to give 173 mg of the desired product as free base used as is (56% yield). LCMS (m/z): 234.2 (MH+), 0.43 min; 1H NMR (400 MHz, DMSO-d6) δ ppm 8.01 (d, J=1.2 Hz, 1H), 7.80 (d, J=1.2 Hz, 1H), 6.33 (s, 2H), 6.27 (t, J=3.9 Hz, 1H), 3.89 (s, 4H), 2.52 (d, J=1.6 Hz, 2H), 2.33 (br. s., 2H), 1.76 (t, J=6.7 Hz, 2H).

Workup

  1. customThe reaction was microwaved at 120° C. for 15 min
  2. washwashed with water (1×), dried sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated to residue
  5. customThe crude was purified by silica gel chromatography
  6. washeluting with 10-90% ethyl acetate and heptane
  7. concentrationThe desired fractions were concentrated to constant mass

Sources & evidence

ORD record
ord-3a15b5e1ccb64e44b536f38a4dcda70f
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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