Boron trifluoride etherate → 2-Diphenylphosphino-dimethylaminoferrocene

HRID 1014756Notes

Reaction equation

HRID 1014756 reaction equation
[CH3:1][N:2]([C-:4]1[CH:8]=[CH:7][CH:6]=[CH:5]1)[CH3:3].[CH-:9]1[CH:13]=[CH:12][CH:11]=[CH:10]1.[Fe+2:14].B(F)(F)F.CCOCC.[Li]CCCC.[P:29](Cl)([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>C1COCC1.CCOCC>[C:36]1([P:29]([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:5]2[C-:4]([N:2]([CH3:3])[CH3:1])[CH:8]=[CH:7][CH:6]=2)[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=1.[CH-:9]1[CH:13]=[CH:12][CH:11]=[CH:10]1.[Fe+2:14]

Participants

7

Reactant 4

HCID 8000Boron trifluoride etherateHCID 66180ChlorodiphenylphosphineHCID 129678476cyclopenta-1,3-diene;N,N-dimethylcyclopenta-2,4-dien-1-amine;iron(2+)HCID 178418339Butyllithium

Product 1

HCID 1317290462-Diphenylphosphino-dimethylaminoferroceneYield 77%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 11 (229 mg, 1.00 mmol) in THF (10 mL) was sequentially treated with BF3.OEt2 (0.13 mL, 1.05 mmol), n-BuLi (0.45 mL, 2.45 M, 1.10 mmol) and Ph2PCl (0.22 mL, 1.20 mmol). Standard workup followed by column chromatography of the pre-adsorbed product (silica gel, Et2O) gave an orange solid. Recrystallization from Et2O afforded 12f (317 mg, 77%) as orange needles in two crops; mp 146-148° C. (Et2O); IR (KBr) vmax 3090, 3050, 2952, 2840, 2780, 1494 cm−1; 31P NMR (121.5 MHz, CDCl3) −20.37; 1H NMR (600 MHz, CDCl3) 7.55-7.52 (m, 2H), 7.39 (m, 3H), 7.28 (m, 5H), 4.20 (s, 1H), 4.13 (s, 5H), 4.10 (t, 1H, J=2.4 Hz), 3.50 (s, 1H), 2.69 (s, 6H) ppm; 13C NMR (150.9 MHz, CDCl3) 139.8 (d, J=11.0 Hz), 137.9 (d, J=10.6 Hz), 135.3 (d, J=22.6 Hz), 132.4 (d, J=18.1 Hz), 129.0, 128.1 (d), 128.0 (d), 127.8, 119.0 (d, J=18.1 Hz), 68.7, 68.5 (d, J=3.0 Hz), 65.9 (d, J=10.6 Hz), 65.2, 60.1, 45.5 ppm; EIMS [m/z (%)] 413 (M+, 100); HRMS (EI) calcd for C24H24NP56Fe: 413.0995. Found 413.0991. Anal. Calcd for C24H24NPFe: C, 69.75; H, 5.85. Found: C, 69.87; H, 5.94.

Workup

  1. customgave an orange solid
  2. customRecrystallization from Et2O

Sources & evidence

ORD record
ord-4dfada01ac624badae251735df5856cd
Source dataset
uspto-grants-2011_07
Patent number
US07982064B2

Reaction notes

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