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

HRID 1603304Notes

Reaction equation

HRID 1603304 reaction equation
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9].[F:10][C:11]1[C:16]([F:17])=[C:15]([O:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH:14]=[CH:13][C:12]=1[C:27]1[N:32]=[CH:31][C:30](Br)=[CH:29][N:28]=1>C(NC(C)C)(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:10][C:11]1[C:16]([F:17])=[C:15]([O:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH:14]=[CH:13][C:12]=1[C:27]1[N:32]=[CH:31][C:30]([C:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])=[CH:29][N:28]=1

Participants

6

Reactant 2

HCID 189371-NonyneHCID 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 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 7912DiisopropylamineSolvent

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 dichoromethane) 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 (6H, m), 1.20-1.55 (18H, m), 1.64 (2H, quint, J7, CH2CH2C≡C), 1.85 (2H, quint, J7, OCH2CH2), 2.46 (2H, t, J7, CH2C≡C), 4.10(2H, t, J7, OCH2), 6.83 (1H, ddd, J8, 7 and 2, 5'-H), 7.85 (1H, ddd, J8, 7 and 2, 6'-H) and 8.79 (2H, 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-76c9b6f9f59746cfb2785028f135bd38
Source dataset
uspto-grants-1999_11
Patent number
US05986096

Reaction notes

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