Laurent Caron et al.
COMMUNICATIONS
3
(s, C4’), 127.2 (s, C5’), 127.5 (d, JP-C ¼5 Hz, C8’), 129.0 (d,
In conclusion, we have demonstrated that formation
of catalytically active second-sphere adducts between
water-soluble organometallic complex and CD is possi-
ble by finely designing the structure of the water-soluble
phosphane. Studies are currently in progress to immobi-
lize supramolecular water-soluble homogeneous cata-
lysts on supports containing CDs.
3JP-C ¼6 Hz, C13’), 129.3 (s, C14’), 134.2 (d, JP-C ¼19 Hz,
2
2
1
C12’), 134.6 (d, JP-C ¼20 Hz, C9’), 136.1 (d, JP-C ¼20 Hz,
1
C10’), 137.8 (d, JP-C ¼11 Hz, C11’), 138.1 (s, C6’), 141.8 (s,
C7’), 151.1 (s, C3’); 31P{1H} NMR (121.49 MHz, CDCl3,
298 K): d¼ À6.07 (s); anal. (%): calcd. for C28H27P (M¼
394 g·molÀ1): C 85.28, H 6.85; found: C 84.90, H 6.64.
Bis(3-sodium sulfonatophenyl)-[4-(4-tert-
butylphenyl)phenyl]phosphine (1)
Experimental Section
[p-(p-t-BuC6H4)Ph]P(Ph)2 (8 g, 20.3 mmol) was dissolved in
11.6 mL of 100% concentrated sulfuric acid obtained by mix-
ture of 9.2 mL of concentrated sulfuric acid (18 N, 96%) and
2.4 mL of oleum (65%). After cooling to 58C, the oleum
(65%, 16.5 mL) was added slowly under vigorous stirring and
keeping the temperature below 108C. The reaction mixture
was then kept at room temperature for 20 hours under a nitro-
gen atmosphere. Excess of oleum was neutralized by addition
of 12 mL of degassed water. The mixture was poured into a
mixture of ice and water (300 g/300 mL), and dipentylamine
(6.38 g, 40.62 mmol) was then added. The ammonium salt of
the sulfonated phosphine was recovered from the acidic aque-
ous layer by addition of ethyl acetate (4ꢀ50 mL). The organic
phase was washed with water up to neutral pH, dried over an-
hydrous MgSO4, filtered and concentrated by rotary evapora-
tion. The resulting solid was then dissolved in isoamyl alcohol
and extracted 20 times with 20 mL of an NaOH solution
(0.07 N). Each fraction was analyzed by 31P{1H} NMR spectro-
scopy. The fractions where a unique signal at À4.72 ppm was
observed were concentrated under vacuum and a white solid
was obtained. This solid was recrystallized from methanol to
give white crystals. Yield: 1.8 g (15%). The notation used in
NMR assignments of 1 is indicated below:
General Remarks
1
The H, 31P and 13C NMR spectra were recorded at 300.13,
121.49 and 75.46 MHz, respectively, on a Bruker Avance 300
DPX instrument. IR spectra were recorded on a Vector 22
Bruker spectrometer. Elemental analyses were performed by
the department of Micro-Analyses at the University of Artois
using an EA 1110 CHNS Thermoquest instrument. Gas chro-
matographic analyses were carried out on a Shimadzu GC-
17A gas chromatograph equipped with a methyl silicone capil-
lary column (25 mꢀ0.25 mm) and a flame ionization detector
(GC:FID). Palladium acetate, b-CD and methylated b-CD
were purchased from Aldrich. The methylated b-CD was a na-
tive b-CD partially O-methylated with statistically 1.8 OH
groups modified per glucopyranose unit. 1-Bromo-4-(4-tert-
butylphenyl)benzene was synthesized as reported in the litera-
ture.[13]
[4-(4-tert-Butylphenyl)phenyl]diphenylphosphine
This was obtained on a multigram scale by a modified publish-
ed procedure.[14] To a suspension of magnesium (1.84 g,
76 mmol, 1.1 equivs.) in 50 mL of anhydrous THF was intro-
duced under nitrogen 1-bromo-4-(4-tert-butylphenyl)benzene
(6.67 g, 23 mmol, 0.33 equivs.). After a few minutes, the reac-
tion began and 13.34 g (46 mmol, 0.66 equivs.) of 1-bromo-4-
(4-tert-butylphenyl)benzene in THF (20 mL) were added
dropwise. The reaction mixture was then heated under reflux
for 1 hour. After cooling, chlorodiphenylphosphine (12.93 g,
58.65 mmol, 0.85 equivs.) in THF (10 mL) was added dropwise
and then heated under reflux for 1 hour. Once the reaction was
complete, the mixture was poured into a mixture of ice (ca
100 g) and HCl (100 mL, 1 N). The aqueous phase was extract-
ed twice with toluene (3ꢀ35 mL) and the combined organic
layers were dried over anhydrous MgSO4, filtered and concen-
trated by rotary evaporation. The resulting oil was recrystal-
lized from ethanol to give white crystals. Yield: 17.3 g (75%).
Thenotation used in NMRassignments of phosphineis indicat-
ed below:
1H NMR (300.13 MHz, D2O, 298 K): d¼0.88 (s, 9H, H1’),
3
3
3
3
6.95 (t, JH-H ꢁ JP-H ¼7.5 Hz, 2H, H9’), 7.05 (t, JH-H ꢁ JP-H
¼
3
7.5 Hz, 2H, H16’), 7.11 (d, JH-H ¼7.5 Hz, 2H, H5’), 7.2–7.3
3
3
(m, 6H, H4’,8’,15’), 7.62 (d, JH-H ꢁ JP-H ¼7.8 Hz, 2H, H12’),
7.67 (d, 3JH-H ¼7.8 Hz, 2H, H14’); 13C{1H} NMR (75.47, MHz,
3
D2O, 298 K): d¼30.6 (s, C1’), 35.2 (s, C2’), 122.0 (d, JP-C
¼
8 Hz, C8’), 126.4 (s, C14’), 128.0 (s, C7’), 130.0 (d, 3JP-C ¼7 Hz,
2
1
C15’), 130.7 (d, JP-C ¼28 Hz, C12’), 132.0 (d, JP-C ¼6 Hz,
2
C10’), 132.2 (s, C4’), 136.1 (d, JP-C ¼20 Hz, C16’), 136.2 (s,
2
C6’), 136.4 (s, C5’), 137.2 (d, JP-C ¼18 Hz, C9’), 139.3 (d,
1JP-C ¼7 Hz, C11’), 143.9 (d, JP-C ¼7 Hz, C13’), 155.9 (s, C3’);
3
31P{1H} NMR (121.49 MHz, D2O, 298 K): d¼ À4.72 (s); FT-
IR: (KBr): n¼2962 (m), 1460 (w), 1304 (m), 1221 (s), 1195
(s), 1079 (w), 1040 (m), 1001 (w), 787 (m), 719 (w), 676 (w),
624 (w), 520 cmÀ1 (w); anal. (%): calcd. for C28H25Na2O6PS2 ·
4 H2O (M¼670 g·molÀ1): C 50.15, H 4.92; found: C 49.74, H
4.31.
1H NMR (300.13 MHz, CDCl3, 298 K): d¼1.38 (s, 9H, H1’),
7.3–7.5 (m, 18H, H4’,5’,8’,9’,12’,13’,14’); 13C{1H} NMR (75.47,
MHz, CDCl3, 298 K): d¼31.7 (s, C1’), 34.7 (s, C2’), 126.3
1454
ꢁ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2004, 346, 1449–1456