2,6-Di-tert-butyl-4-methylphenol → HCID 68709855, compound

HRID 222136Notes

Reaction equation

HRID 222136 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:10](I)=[C:9]([C:12]2[C:17](Br)=[CH:16][N:15]=[C:14]([NH2:19])[N:13]=2)[NH:8][C:7]=1[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:5])[CH3:2].[CH:26]([Sn](CCCC)(CCCC)CCCC)=[CH2:27].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:3][C:4]([C:6]1[C:10]2=[CH:26][CH:27]=[C:17]3[C:12]([N:13]=[C:14]([NH2:19])[N:15]=[CH:16]3)=[C:9]2[NH:8][C:7]=1[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998TributylvinyltinHCID 68707177HCID 68707177, compound

Product 1

HCID 68709855HCID 68709855, compoundYield 30.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 5-(2-amino-5-bromo-pyrimidin-4-yl)-4-iodo-2-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester (XXVIIA, R2=phenyl, R3=COOEt, 0.099 mmol) in dioxane (4 mL), under argon, vinyltributyltin (0.099 mmol), 2,6-di-tert-butyl-4-methylphenol (0.0045 mmol) and Pd(Ph3P)4 (0.01 mmol) were added. The reaction mixture was heated at 110° C. for 3 h, cooled to rt, the precipitate filtered through a celite pad and the resulting solution evaporated to dryness. The residue was chromatographed on silica gel (eluant: AcOEt/hexane 4:1) affording the title compound (0.03 mmol, 30% yield), ESI (+) MS: m/z 333 (MH+). 1H NMR: 1.20 (t, J=7.03, 3H), 4.19 (q, J=7.03, 2H), 6.55 (bs, 2H), 7.50 (d, J=8.60, 1H), 7.53-7.70 (m., 5H), 7.90 (d, J=8.60, 1H), 9.07 (s, 1H), 12.93 (s, 1H), and 5-amino-8-methylene-2-phenyl-3,8-dihydro-3,4,6-triaza-cyclopenta[a]indene-1-carboxylic acid ethyl ester (0.024 mmol) (XXVIII, R2=phenyl, R3=COOEt), ESI (+) MS: m/z 333 (MH+). 1H NMR: 1.14 (t, J=7.07 Hz, 3H), 4.16 (q, J=7.07 Hz, 2H), 6.02 (d, J=1.32, 1H), 6.43 (d, J=1.32, 1H), 6.57 (bs, 2H), 7.40-7.46 (m, 2H), 7.52-7.66 (m, 3H), 8.44 (s, 1H), 12.74 (s, 1H).

Workup

  1. temperaturecooled to rt
  2. filtrationthe precipitate filtered through a celite pad
  3. customthe resulting solution evaporated to dryness
  4. customThe residue was chromatographed on silica gel (eluant: AcOEt/hexane 4:1)

Sources & evidence

ORD record
ord-0e790377339b49f7adf00dcbac3a9dcf
Source dataset
uspto-grants-2012_06
Patent number
US08207180B2

Reaction notes

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