Diisopropylamine → 2-(2',3'-Difluoro-4'-octyloxyphenyl)-5-non-1-ynylpyrimidine

HRID 1954506Notes

Reaction equation

HRID 1954506 reaction equation
[F:1][C:2]1[C:7]([F:8])=[C:6]([O:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:5]=[CH:4][C:3]=1[C:18]1[N:23]=[CH:22][C:21](Br)=[CH:20][N:19]=1.C(N[CH:29]([CH3:31])[CH3:30])(C)C>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.[Cu]I>[F:1][C:2]1[C:7]([F:8])=[C:6]([O:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:5]=[CH:4][C:3]=1[C:18]1[N:23]=[CH:22][C:21]([C:7]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:31][CH2:29][CH3:30])=[CH:20][N:19]=1

Participants

5

Reactant 2

HCID 7912DiisopropylamineHCID 232970432-(2',3'-Difluoro-4'-octyloxyphenyl)-5-bromopyrimidine

Product 1

HCID 544551022-(2',3'-Difluoro-4'-octyloxyphenyl)-5-non-1-ynylpyrimidineYield 92%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

-Non-1-yne (1.0 ml, 6.4 mmol) was added via syringe to degassed mixture of 2-(2',3'-difluoro-4'-octyloxyphenyl)-5-bromopyrimidine 4 (1.27 g, 3.18 mmol), tetrakis(triphenylphosphine)palladium (173 mg, 0.15 mmol) and copper(I) iodide (29 mg, 0.15 mmol) in diisopropylamine (60 ml) under nitrogen. The mixture was heated under gentle reflux for 4 h. The solvent was removed in vacuo and the residue was purified by flash chromatography (5% ethyl acetate-light petroleum, the sample was preloaded onto silica in dichloromethane) to give the nonynylpyrimidine 38 (1.29 g, 92%) (from MeOH), transitions/° C. K 64.4 (N 63.3) I; νmax /cm-1 (KBr) 2920, 2850, 2220, 1615, 1520, 1470, 1430s, 1295, 1205 and 1090s; δ 0.90 (6 H, m), 1.20-1.55 (18 H, m), 1.64 (2 H, quint, J 7, CH2CH2C≡C), 1.85 (2 H, quint, J 7, OCH2CH2), 2.46 (2 H, t, J 7, CH2C≡C), 4.10 (2 H, t, J 7, OCH2), 6.83 (1H, ddd, J 8, 7 and 2, 5'-H), 7.85 (1H, ddd, J 8, 7 and 2, 6'-H_ an d8.79 (2 H, s, 4- and 6-H), m/z 442 (M+), 330, 288, 287, 274, 273, 247 and 220.

Workup

  1. customto degassed
  2. temperatureThe mixture was heated
  3. temperatureunder gentle reflux for 4 h
  4. customThe solvent was removed in vacuo
  5. customthe residue was purified by flash chromatography (5% ethyl acetate-light petroleum

Sources & evidence

ORD record
ord-84f4ae716a124929961ece361f772e4b
Source dataset
uspto-grants-2000_09
Patent number
US06121448

Reaction notes

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