Aniline → HCID 10774783, compound

HRID 1949619Notes

Reaction equation

HRID 1949619 reaction equation
CC(C)([O-])C.[Na+].[CH2:7]([C:10]1[CH:15]=[CH:14][C:13](Br)=[CH:12][CH:11]=1)[CH:8]=[CH2:9].[NH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[CH2:7]([C:10]1[CH:15]=[CH:14][C:13]([NH:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:12][CH:11]=1)[CH:8]=[CH2:9]

Participants

6

Reactant 3

HCID 6115AnilineHCID 137529Benzene, 1-bromo-4-(2-propenyl)-HCID 23676156Sodium t-butoxide

Product 1

HCID 10774783HCID 10774783, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

Tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3, 0.2623 g, 2.864×10−4 mol] and tri-tert-butylphosphine (0.11 g, 5.437×10−4 mol) were weighed out in a glove box, transferred to a Schlenk line, and stirred for about 5 min in hexanes before adding sodium tert-butoxide (2.000 g, 2.081×10−2 mol) as a slurry in hexanes, Compound 1 (2.810 g, 1.426×10−2 mol), and 80 mL hexanes. Next, distilled aniline (1.43 mL, 1.57×10−2 mol) was added over a period of about 3 min with stirring. A brown precipitate formed after about 5 min at room temperature, and stirring was halted after 2 h. The mixture was then filtered through Celite, and the hexanes were removed in vacuo at ≦45° C. so as to minimize allyl group isomerization. The resulting oil was then placed in a freezer at −23° C. for 1 h to solidify. The resulting solid was then recrystallized from pentane to yield light tan crystals of Compound 2 (2.43 g, 82% yield) that were collected by filtration and rinsed 3× with cold pentane. GC/MS: single peak; m/z (rel. intensity) 210 (M+ +H, 17), 209 (M+, 100), 208 (M+ −H, 29), 182 (38) 117 (33). 1H NMR (CDCl3): δ7.24 (m, 2H), 7.09 (d, J=8.5 Hz, 2H), 7.04 (d, J=6.5 Hz, 2H), 7.03 (d, J=6.5 Hz, 2H), 6.89 (t, J=7 Hz, 1 H), 5.94 (m, 1H), 5.64 (s, 1H), 5.06 (m, 2H), 3.34 (d, J=6.5 Hz, 2H). 13C NMR (CD2Cl2): δ144.0, 141.4, 138.4, 133.3, 129.7, 129.6, 120.7, 118.7, 117.3, 115.5, 39.8. EA for C15H15N: Calc. %: C, 86.08; H, 7.22; N, 6.69; Found %: C, 85.95; H, 7.11; N, 6.82.

Workup

  1. customtransferred to a Schlenk
  2. additionwas added over a period of about 3 min
  3. customA brown precipitate formed after about 5 min at room temperature
  4. stirringstirring
  5. filtrationThe mixture was then filtered through Celite
  6. customthe hexanes were removed in vacuo at ≦45° C. so as
  7. waitThe resulting oil was then placed in a freezer at −23° C. for 1 h
  8. customThe resulting solid was then recrystallized from pentane

Sources & evidence

ORD record
ord-e4f9746acbc0471fb0f2cd24f2433b81
Source dataset
uspto-grants-2013_03
Patent number
US08399761B2

Reaction notes

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