Tert-Butylamine → HCID 90041146, compound

HRID 523019Notes

Reaction equation

HRID 523019 reaction equation
[Br:1][C:2]1[N:3]=[C:4]2[C:11]([C:12]([OH:14])=O)=[CH:10][N:9]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:5]2=[N:6][C:7]=1[CH3:8].CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CN(C(N(C)C)=[N+]1C2C=CC=CC=2[N+]([O-])=N1)C.F[P-](F)(F)(F)(F)F.C(N(CC)CC)C.[C:78]([NH2:82])([CH3:81])([CH3:80])[CH3:79]>C(OCC)(=O)C.CN(C)C=O>[C:78]([NH:82][C:12]([C:11]1[C:4]2[C:5](=[N:6][C:7]([CH3:8])=[C:2]([Br:1])[N:3]=2)[N:9]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[CH:10]=1)=[O:14])([CH3:81])([CH3:80])[CH3:79]

Participants

9

Reactant 6

HCID 6385Tert-ButylamineHCID 8471TriethylamineHCID 9886HexafluorophosphateHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 90040678HCID 90040678, compoundHCID 178484288HCID 178484288, compound

Product 1

HCID 90041146HCID 90041146, compoundYield 92.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 2-bromo-3-methyl-5-(2-trimethylsilanyl-ethoxymethyl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylic acid (1.16 g, 3 mmol), HBTU [1-[bis(dimethylamino)methylene]-1H-benzotriazolium 3-oxide, hexafluorophosphate(1-) (1:1) (1.48 g, 3.9 mmol), N,N-dimethylformamide (12 mL) and triethylamine (0.61 g, 6 mmol) was stirred at room temperature for 1 h, and then tert-butylamine (0.63 mL, 6 mmol) was added. The mixture was stirred an additional hour and then diluted with ethyl acetate, washed once with 0.5 M sodium carbonate, twice with water, once with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification by chromatography (silica, 20% ethyl acetate in hexanes) gave 2-bromo-3-methyl-5-(2-trimethylsilanyl-ethoxymethyl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylic acid tert-butylamide (1.22 g, 92%) as a white crystalline solid. 1H NMR (400 MHz, DMSO-d6) δ ppm −0.09 (s, 9H), 0.83 (t, J=8.2 Hz, 2H), 1.43 (s, 9H), 2.71 (s, 3H), 3.54 (t, J=8.2 Hz, 2H), 5.64 (s, 2H), 7.64 (s, 1H), 8.49 (s, 1H).

Workup

  1. stirringThe mixture was stirred an additional hour
  2. washwashed once with 0.5 M sodium carbonate, twice with water, once with brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurification by chromatography (silica, 20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-5e10cc64ec6f4480b93afd57d84727c4
Source dataset
uspto-grants-2016_05
Patent number
US09334278B2

Reaction notes

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