Chlorodiphenylphosphine → HCID 5017640, compound

HRID 2303740Notes

Reaction equation

[CH:1]1([Tl])[CH:5]=[CH:4][CH:3]=[CH:2]1.[C:7]1([P:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)Cl)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>C(OCC)C>[C:15]1([P:13]([C:2]2[CH2:1][CH:5]=[CH:4][CH:3]=2)[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1

Participants

Conditions

Temperature: 0 °C

Procedure

50 g (0.186 moles) of cyclopentadienylthallium (obtained from Fluka) were placed in a 500 ml flask together with 300 ml of diethyl ether. The suspension was cooled to 0° C. and 34.2 ml (0.186 moles) of diphenylchlorophosphine were added dropwise over 10 minutes. The suspension was then heated to room temperature, stirred for one hour and finally filtered through a frit. The solvent was then stripped off under vacuum to leave 39.5 g (85% of the theoretical yield) of the intermediate diphenylphosphinocyclopentadiene, compound 2. An 18.6 g portion (0.074 moles) of compound 2 was then diluted with toluene and cooled to 0° C. 33.2 ml of a 2.24 molar solution of butyllithium in hexane (0.074 moles) were added to this solution over 10 minutes. After being heated to room temperature and stirred for 2 hours, the yellow solution produced a precipitate, which was filtered off and washed with toluene and then with hexane. After drying under vacuum, 13.2 g of compound 3 (70% of the theoretical yield) were obtained in the form of a brownish powder (cf. J. Am. Chem. Soc. 105, (1983), 3882; Organometallics 1, (1982), 1591). 1H NMR (400 MHz, THF-d8): δ=7.3 (m, 4H); 7.15 (m, 6H); 5.96 (m, 2H); 5.92 (m, 2H); 31P NMR (161.9 MHz, THF-d8): δ=−20.

Workup

temperatureThe suspension was then heated to room temperature
filtrationfinally filtered through a frit
customto leave 39.5 g (85% of the

Sources & evidence

ORD record: ord-107a0b2fa2a24768b7c32d2697363104
Source dataset: uspto-grants-2002_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06433112B1

Reaction notes

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