Additions of PH3 to Monosubstituted Alkenes of the Formula H2C=CH(CH2)x(CF2)yCF 3: Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities

Article abstract of DOI:10.1021/jo980692y

Reactions of PH₃ and commercially available H₂C=CHR_f(R_f6/8/10 = (CF₂)₅CF₃/(CF₂)₇CF ₃/(CF₂)₉CF₃) give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80-90°C), the phosphines P(CH₂CH₂R_f)₃ (1-3; 63-75%). Analogous reactions with H₂C=CHCH₂R_f8 (7) and H₂C=CHCH₂CH₂R_f8 (10) give P(CH₂CH₂CH₂R_f8)₃ (4, 73%) and P(CH₂CH₂CH₂CH₂R_f8) ₃ (5, 66%), in which the phosphorus is increasingly insulated from the electronegative R_f moiety. The alkenes 7 and 10 are prepared from Bu₃SnCH₂CH=CH₂ and IR_f8 (hv, CH₂Cl₂, 81%) or ICH₂R_f8 (VAZO, refluxing CF₃C₆H₅, 56%). The reaction of 1 and H₂O₂ gives O=P(CH₂CH₂R_f6)₃ (6, 88%), which can be reduced with HSiCl₃ to 1. Partition coefficients (CF₃C₆F₁₁/toluene, 27°C) range from 98.8:1.2 (1, 4) through 98.9:1.1 (5) to >99.7:<0.3 (2, 3, 6). Crystals of 4 diffract poorly, but a packing motif that maximizes interactions between R_f segments is evident.

Full text of DOI:10.1021/jo980692y

6302
J . Org. Chem. 1998, 63, 6302-6308
Ad d ition s of P H3 to Mon osu bstitu ted Alk en es of th e F or m u la
H2CdCH(CH2)x(CF 2)yCF 3: Con ven ien t, Mu ltigr a m Syn th eses of a
F a m ily of P a r tia lly F lu or in a ted Tr ia lk ylp h osp h in es w ith
Mod u la ted Electr on ic P r op er ties a n d F lu or ou s P h a se Affin ities
Luke J . Alvey, Drew Rutherford, J errick J . J . J uliette, and J . A. Gladysz*,†
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112
Received April 14, 1998
Reactions of PH3 and commercially available H2CdCHRf (Rf6/8/10 ) (CF2)5CF3/(CF2)7CF3/(CF2)9CF3)
give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80-90 °C), the
phosphines P(CH2CH2Rf)3 (1-3; 63-75%). Analogous reactions with H2CdCHCH2Rf8 (7) and
H2CdCHCH2CH2Rf8 (10) give P(CH2CH2CH2Rf8)3 (4, 73%) and P(CH2CH2CH2CH2Rf8)3 (5, 66%), in
which the phosphorus is increasingly insulated from the electronegative Rf moiety. The alkenes 7
and 10 are prepared from Bu3SnCH2CHdCH2 and IRf8 (hν, CH2Cl2, 81%) or ICH2Rf8 (VAZO,
refluxing CF3C6H5, 56%). The reaction of 1 and H2O2 gives OdP(CH2CH2Rf6)3 (6, 88%), which can
be reduced with HSiCl3 to 1. Partition coefficients (CF3C6F11/toluene, 27 °C) range from 98.8:1.2
(1, 4) through 98.9:1.1 (5) to >99.7:<0.3 (2, 3, 6). Crystals of 4 diffract poorly, but a packing motif
that maximizes interactions between Rf segments is evident.
One of the most innovative new approaches to catalysis
complexes as catalysts,4b as well as many reactions
catalyzed by phosphines alone.5
involves perfluorinated or “fluorous”1-3 solvents such as
perfluoroalkanes, perfluoroethers, and perfluoroamines.
As detailed in a series of articles by Horva´th,1,2 this
protocol exploits the temperature-dependent miscibility
of fluorous and organic solvents. Many combinations
afford bilayers at room temperature, but one phase at
higher temperatures. Accordingly, catalysts that have
high affinities for fluorous media offer unique possibili-
ties. As shown in Figure 1, they may react under
homogeneous conditions in the high temperature mon-
ophasic limit and easily be recovered in the low-temper-
ature biphasic limit. This design element combines the
best features of homogeneous and heterogeneous cat-
alysts.4a
In separate and collaborative investigations, we and
Horva´th have shown that rhodium complexes containing
the partially fluorinated trialkylphosphine P(CH2-
CH2(CF2)5CF3)3 or “P(CH2CH2Rf6)3” (1) catalyze a variety
of transformations, have high affinities for fluorous
media, and can be easily recovered and recycled.1,6-8 In
this paper, we describe convenient, large scale prepara-
tions of 1 and homologues in which the six-carbon
perfluoroalkyl segment is lengthened (2, Rf8; 3 Rf10). We
also describe syntheses of homologues in which the (CH2)2
spacer segment is lengthened (4, (CH2)3Rf8; 5, (CH2)4Rf8).
The resulting series of phosphines (Chart 1) features
gradually modulated donor strengths, as well as fluorous
phase affinities. Together, they constitute a valuable
“toolkit” for the systematic development of catalytic
reactions based upon fluorous trialkylphosphines or their
metal complexes.
Other results reported below include (1) the synthesis
and reduction of the fluorous phosphine oxide OdP(CH2-
CH2Rf6)3 (6), (2) partition coefficients that quantify the
affinities of 1-6 for fluorous media, and (3) partial
crystallographic data for 4. Additional syntheses of 1
have been described by other investigators,9 and alterna-
tive routes to fluorous trialkylphosphines developed in
our laboratory will be detailed separately.10 Metal tri-
arylphosphine catalysts that feature one pony tail per
To achieve high fluorous phase affinities, Horva´th
proposed that catalysts be derivatized with “pony tails”s
substituents such as (CH2)x(CF2)yCF3.1 The perfluoro-
alkyl or Rf(y+1) segments serve, when of sufficient length
and number, a “like dissolves like” function. Further-
more, the (CH2)x “spacer” segments can provide tuning
elements. At higher values of x, the reaction center will
be insulated from the electron withdrawing Rf(y+1) moi-
eties. At lower values, the Lewis acidity will be en-
hanced. Phosphines would constitute an obvious testing
ground for this concept, since there are a large number
of important processes that utilize metal phosphine
† New address: Institut fu¨r Organische Chemie, Friedrich-Alex-
ander Universita¨t Erlangen-Nu¨rnberg, Henkestrasse 42, D-91054
Erlangen, Germany.
(1) (a) Horva´th, I. T.; Raba´i, J . Science 1994, 266, 72. (b) Horva´th,
I. T.; Kiss, G.; Cook, R. A.; Bond, J . E.; Stevens, P. A.; Raba´i, J .;
Mozeleski, E. J . J . Am. Chem. Soc. 1998, 120, 3133.
(2) Horva´th, I. T. Acc. Chem. Res. 1998, 31, 1, in press.
(3) Additional perspectives: (a) Gladysz, J . A. Science 1994, 266,
55. (b) Studer, A.; Hadida, S.; Ferritto, R.; Kim, S.-Y.; J eger, P.; Wipf,
P.; Curran, D. P. Science 1997, 275, 823. (c) Cornils, B. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 2057; Angew. Chem. 1997, 109, 2147.
(4) Applied Homogeneous Catalysis with Organometallic Com-
pounds; Cornils, B., Herrmann, W. A., Eds.; VCH Publishers: New
York, 1996. See (a) Vol. 2, Ch. 3.1.1. (b) Vol. 1, Ch. 2.2, 2.3, 2.5, 2.6,
2.9.
(5) Representative examples: (a) Basavaiah, D.; Rao, P. D.; Hyma,
R. S. Tetrahedron 1996, 52, 8001. (b) Zhu, G.; Chen, Z.; J iang, Q.; Xiao,
D.; Cao, P.; Zhang, X. J . Am. Chem. Soc. 1997, 119, 3836.
(6) (a) J uliette, J . J . J .; Horva´th, I. T.; Gladysz, J . A. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 1610; Angew. Chem. 1997, 109, 1682. (b)
J uliette, J . J . J .; Rutherford, D.; Horva´th, I. T.; Gladysz, J . A.,
manuscript in preparation.
(7) Rutherford, D.; J uliette, J . J . J .; Rocaboy, C.; Horva´th, I. T.;
Gladysz, J . A. Catal. Today 1998, 42, 381.
(8) Dinh, L., unpublished results, University of Utah.
(9) (a) Benefice-Malouet, S.; Blancou, H.; Commeyras, A. J . Fluorine
Chem. 1985, 30, 171. (b) Langer, F.; Pu¨ntener, K.; Stu¨rmer, R.;
Knochel, P. Tetrahedron: Asymmetry 1997, 8, 715. (c) Battacharyya,
P.; Gudmunsen, D.; Hope, E. G.; Kemmitt, R. D. W.; Paige, D. R.;
Stuart, A. M. J . Chem. Soc., Perkin Trans. 1 1997, 3609.
S0022-3263(98)00692-6 CCC: $15.00 © 1998 American Chemical Society
Published on Web 09/04/1998

Additions of PH3 to Monosubstituted Alkenes
J . Org. Chem., Vol. 63, No. 18, 1998 6303
F igu r e 1. One possibility for catalysis with fluorous solvents.
Ch a r t 1. Su m m a r y of Abbr evia tion s
Sch em e 1. Syn th eses of F lu or ou s P h osp h in es
w ith (CH2)2 Sp a cer s
This lead was adapted to the syntheses summarized
in Scheme 1. Key design considerations were as fol-
lows: (1) a PH3/H2CdCHRf stoichiometry of approxi-
mately 1:3 was employed, (2) temperatures of 80-85 °C
were used to moderate the rate of AIBN decomposition,15
(3) the initial mixture of primary, secondary, and tertiary
phosphines was treated with a second alkene charge (4-
20% of the first charge) and the less reactive initiator
VAZO.15 It was thought that slower initiation rates
might minimize any independent polymerization of the
alkene, which is at higher concentration than PH3 after
the first charge and may be in excess over phosphorus-
hydrogen bonds after the second charge.
Gratifyingly, analytically pure 4-8 g quantities of the
CH2CH2Rf6, CH2CH2Rf8, and CH2CH2Rf10 substituted
phosphines 1-3 could be isolated in 63-75% yields based
upon the total alkene utilized. Since 1-3 constitute 85-
90% of the crude phosphine products after the first alkene
charge, comparable yields might be possible at that stage.
However, complicated or tedious workups would likely
be required. The phosphines 1-3 showed progressive
increases in melting points (liquid, 47-48 °C, 102-103
°C) and decreases in CF3C6F11 solubilities. No other
phase transitions were evident by DSC. Needles of 2
could be grown from CF3C6H5/toluene, but were unfor-
tunately too thin for crystallography. All compounds
survived vacuum distillation, and mass spectra (EI)
exhibited intense molecular ions.
aryl ring have also recently been reported,11 as well as a
number of fluorous catalysts that are not phosphine
based.12
Resu lts
1. Rea ction s of P H3 a n d H2CdCHRf. Free radical
chain additions of phosphorus-hydrogen bonds to alk-
enes are well-known.13 Since many alkenes of the
formula H2CdCHRf are commercially available, this
represents an obvious approach to the title compounds.
Indeed, a preliminary study of the reaction of PH3 gas14
and H2CdCHRf6 was found to give the fluorous phosphine
1 in 26% yield.1a The synthesis was conducted at 100
°C in an autoclave in the presence of the initiator AIBN
(Chart 1). Small amounts of primary and secondary
phosphine byproducts, PH2(CH2CH2Rf6) and PH(CH2-
CH2Rf6)2, were removed by a second AIBN charge.
(10) Alvey, L. J .; Bernatis, P. B., unpublished results, University of
Utah, and manuscripts in preparation.
(11) (a) Betzemeier, B.; Knochel, P. Angew. Chem., Int. Ed. Engl.
1997, 36, 2623; Angew. Chem. 1997, 109, 2736. (b) See also Kainz, S.;
Baumann, W.; Koch, D.; Leitner, W. Angew. Chem., Int. Ed. Engl. 1997,
36, 1628; Angew. Chem. 1997, 109, 1699.
(12) (a) Klement, I.; Lu¨tjens, H.; Knochel, P. Angew. Chem., Int. Ed.
Engl. 1997, 36, 1454; Angew. Chem. 1997, 109, 1605. (b) Vincent, J .-
M.; Rabion, A.; Yachandra, V. K.; Fish, R. H. Angew. Chem., Int. Ed.
Engl. 1997, 36, 2346; Angew. Chem. 1997, 109, 2438. (c) Ryu, I.;
Niguma, T.; Minakata, S.; Komatsu, M.; Hadida, S.; Curran, D. P.
Tetrahedron Lett. 1997, 38, 7883. (e) Pozzi, G.; Cinato, F.; Montanari,
F.; Quici, S. J . Chem. Soc., Chem. Commun. 1998, 877.
(13) (a) Gilheany, D. G.; Mitchell, C. M. The Chemistry of Organo-
phosphorus Compounds; Hartley, F. R., Ed.; Wiley & Sons: New York,
1990; Vol. 1, p 173. (b) Rauhut, M. M.; Currier, H. A.; Semsel, A. M.;
Wystrach, V. P. J . Org. Chem. 1961, 26, 5138. (c) Hackney, M. L. J .;
Schubert, D. M.; Brandt, P. F.; Haltiwanger, R. C.; Norman, A. D.
Inorg. Chem. 1997, 36, 1867 and references therein. (d) Baxley, G. T.;
Miller, W. K.; Lyon, D. K.; Miller, B. E.; Nieckarz, G. F.; Weakley, T.
J . R.; Tyler, D. R. Inorg. Chem. 1996, 35, 6688.
(14) Ca u tion : PH3 (bp -87.7 °C) is toxic and hazardous and must
be handled in strict accordance with the safety literature. Spontaneous
room temperature ignition normally requires traces of P2H4: (a)
Dictionary of Inorganic Compounds; Chapman & Hall: New York,
1992; Vol. 3, p 3386. (b) Toy, A. D. F. In Comprehensive Inorganic
Chemistry; Bailar, J . C., J r., Emele´us, H. J ., Nyholm, R., Trotman-
Dickenson, A. F., Eds.; Pergamon: Oxford, 1973; Vol. 2, p 414. (c)
Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; Wiley & Sons:
New York, 1994; Vol. 6, p 3160.
(15) Ravve, A. Principles of Polymer Chemistry; Plenum Press: New
York, 1995; p 38.

6304 J . Org. Chem., Vol. 63, No. 18, 1998
Alvey et al.
Sch em e 2. Syn th esis of a F lu or ou s P h osp h in e
w ith (CH2)3 Sp a cer s
The NMR properties of 1-3 were similar, with little
variation due to the lengths of the Rf segments (e.g., 31P
{1H}, δ -25.5 to -25.4, CF3C6F11). The 13C{1H} spectra
showed PCH2 signals that were coupled to phosphorus
but not, within detection limits, to fluorine (δ 16.5-16.4,
1J CP ) 16-17 Hz, w1/2 ) 8.0-8.6 Hz). The PCH2CH2-
2
CF2 signals were downfield (δ 27.6-27.4, J CP ) 20-21
2
Hz; J CF ) 23-24 Hz) and strongly coupled to both
phosphorus and fluorine. The 31P NMR signals of the
primary and secondary phosphine byproducts (Scheme
1) showed the expected multiplicities and chemical shift
trends.16 To ensure accurate ratios, T1 measurements
were made and appropriate spectral parameters uti-
lized.16
Sch em e 3. Syn th esis of a F lu or ou s P h osp h in e
w ith (CH2)4 Sp a cer s
2. Syn th eses an d Reaction s of H2CdCH(CH2)x-2Rf8.
Tri(n-octyl)phosphine contains the same number of car-
bon atoms as 1, but lacks fluorine atoms. Thus, it
constitutes a valuable reference. Iridium carbonyl de-
rivatives, trans-Ir(Cl)(CO)(L)2, of both phosphines have
been characterized.17 The IR νCdO value is significantly
higher for the adduct of 1 (1975 vs 1942 cm-1). Hence,
the (CH2)2 spacers do not completely insulate the iridium
from the electron-withdrawing Rf6 groups. Accordingly,
we sought to extend the preceding syntheses to phos-
phines with longer (CH2)x segments. This in turn re-
quires alkenes with CH2 groups between the vinyl and
Rf moieties.
Such alkenes do not appear to be commercially avail-
able. However, free radical chain additions of perfluo-
roalkyl iodides (IRf) to alkenes are well-known.18 Fur-
thermore, allyl stannanes are frequently used to effect
free radical chain allylations.19 It has been reported that
ICF3 and IRf6 react with the allyl stannane Bu3SnCH2-
CHdCH2 in the presence of a palladium(0) initiator to
give alkenes of the formula H2CdCHCH2Rf.20 Accord-
ingly, IRf8 and Bu3SnCH2CHdCH2 were photolyzed as
shown in Scheme 2. Workup gave H2CdCHCH2Rf8 (7),
which has been prepared previously by different routes,21
in 81% yield on a 12-13 g scale. Then PH3 and 7 were
reacted in a sequence similar to those in Scheme 1. The
phosphine 4, which features (CH2)3 spacer segments, was
isolated as an analytically pure white powder in 73%
yield on a 4-5 g scale.
(16) (a) The following T1 values were measured with standard
software: 5, T1 ) 1.66 ( 0.01 s; PH(CH2CH2CH2CH2Rf8)2 T1 ) 1.47 (
0.04 s; PH2CH2CH2CH2CH2Rf8 T1 ) 2.94 ( 0.07 s. Accordingly,
phosphine ratios were determined using a 45° pulse width, a 10 s
relaxation delay, and a 1.6 s acquisition time. Data for experiments
in Schemes 1-3 follow. (b) 1 (85.2%, δ -25.5), PH(CH2CH2Rf6)2 (9.6%,
A phosphine with still longer spacer segments was
sought. Accordingly, the commercially available alcohol
HOCH2Rf8 was converted to the corresponding triflate 8
in 93% yield as shown in Scheme 3.22 The modest
electrophilicity of 8 as compared to other triflates was
evidenced by its stability to an aqueous workup. Reac-
tion of 8 and KI in refluxing HOCH2CH2OH gave the
iodide ICH2Rf8 (9) in 93% yield on a 25 g scale. A thermal
reaction with Bu3SnCH2CHdCH2, using VAZO as the
initiator, afforded the alkene H2CdCHCH2CH2Rf8 (10)23
in 56% yield on a 5 g scale. Then PH3 and 10 were
reacted in a sequence similar to those in Scheme 1. The
phosphine 5, which features (CH2)4 spacer segments, was
isolated as an analytically pure white powder in 66%
yield on a 4 g scale.
1
1
δ -67.0, d, J HP ) 198 Hz), PH2CH2CH2Rf6 (5.2%, δ -140.8, t, J HP
)
190 Hz). (c) 2 (89.7%, δ -25.4), PH(CH2CH2Rf8)2 (7.4%, δ -67.1, d,
1J HP ) 200 Hz), PH2CH2CH2Rf8 (2.9%, δ -141.0, t, 1J HP ) 192 Hz). (d)
1
3 (90.4%, δ -25.5), PH(CH2CH2Rf10
)
(8.7%, δ -67.1, d, J HP ) 199
2
1
Hz), PH2CH2CH2Rf10 (0.9%, δ -141.0, t, J HP ) 193 Hz). (e) 4 (80.9%,
δ -34.8), PH(CH2CH2CH2Rf8)2 (9.1%, δ -73.4, d, 1J HP ) 193 Hz), PH2-
1
CH2CH2CH2Rf8 (10.0%, δ -145.5, t, J HP ) 190 Hz). (f) 5 (85.1%, δ
1
-32.8), PH(CH2CH2CH2CH2Rf8)2 (6.8%, δ -70.9, d, J HP ) 194 Hz),
1
PH2CH2CH2CH2CH2Rf8 (8.1%, δ -140.8, t, J HP ) 190 Hz).
(17) (a) Guillevic, M.-A.; Arif, A. M.; Horva´th, I. T.; Gladysz, J . A.
Angew. Chem., Int. Ed. Engl. 1997, 36, 1612; Angew. Chem. 1997, 109,
1685. (b) Guillevic, M.-A.; Rocaboy, C.; Arif, A. M.; Horva´th, I. T.;
Gladysz, J . A. Organometallics 1998, 17, 707.
(18) (a) Brace, N. O.; Marshall, L. W.; Pinson, C. J .; van Wingerden,
G. J . Org. Chem. 1984, 49, 2361; Huang, W.-Y.; Zhang, H.-Z. J .
Fluorine Chem. 1990, 50, 133. (b) Feiring, A. E. J . Org. Chem. 1985,
50, 3269.
(19) Keck, G. E.; Enholm, E. J .; Yates, J . B.; Wiley: M. R.
Tetrahedron 1985, 41, 4079.
(20) Matsubara, S.; Mitani, M.; Utimoto, K. Tetrahedron Lett. 1987,
28, 5857.
(21) Earlier syntheses: (a) Umemoto, T.; Kuriu, Y. Tetrahedron Lett.
1981, 22, 5197. (b) Umemoto, T.; Kuriu, Y.; Nakayama, S.-i. Tetrahe-
dron Lett. 1982, 23, 1169. (c) Fuchikami, T.; Ojima, I. Tetrahedron
Lett. 1984, 25, 307. (d) Hu, C.-M.; Qing, F.-L.; Huang, W.-Y. J . Org.
Chem. 1991, 56, 2801. (e) Ame´duri, B.; Boutevin, B.; Nouiri, M.; Talbi,
M. J . Fluorine Chem. 1995, 74, 191. (f) Yamamoto, Y.; Saito, K.
Organometallics 1997, 16, 2207. (g) Napoli, M.; Gambaretto, G. P. J .
Fluorine Chem. 1997, 84, 101.
The phosphines 4 and 5 were characterized identically
to 1-3 above. Together with 2, they define another
homologous series ((CH2)xRf8, x ) 2, 3, 4). They became
more air sensitive as x increases, consistent with an
attenuated electron-withdrawing effect of the Rf8 group.
However, the melting points did not follow an obvious
(22) This compound has been described in patents in the following
Chemical Abstracts citations: (a) Hansen, R. L. 1967, 67, 63788. (b)
Masahiro, I. 1994, 121, 280253. (c) Masahiro, I. 1995, 122, 105246.
(23) This compound has been described once previously in a patent.
Chemical Abstracts citation: Meinert, H. 1997, 126, 250892.

Additions of PH3 to Monosubstituted Alkenes
J . Org. Chem., Vol. 63, No. 18, 1998 6305
F igu r e 2. Packing diagram for P(CH2CH2CH2(CF2)7CF3)3 (4).
trend (47-48 °C, 71.5-72.5 °C, 44.5-45.0 °C). No other
phase transitions were evident by DSC. The solubilities
in toluene progressively increased (2, sparingly soluble
near reflux; 5, very soluble at room temperature). Sur-
prisingly, the 31P NMR chemical shifts did not exhibit a
monotonic trend (δ -25.5, -34.8, -32.8). The 13C NMR
CH2Rf6)2 that were not in the original sample, as well as
other unidentified species.
When hot toluene solutions of 4 were stored at 27 °C,
single crystals formed. Although they diffracted poorly,
data sets were collected using CCD detectors. These
could not be refined to suitable levels for bond length and
angle analyses. However, the packing motif was also of
interest, and a diagram is provided in Figure 2 (key data,
-75 °C: P21/n, Z ) 4, unit cell ca. 23.06 × 6.46 × 32.49
Å). Although each phosphorus is pyramidal, from one
perspective the three pony tails define a T-shape. When
viewed from the plane of the “T”, infinite stacks are
evident. The horizontal part of each “T” defines a “raft”.
These pack back-to-back (“T” under “ ”) along an or-
thogonal axis. Along the remaining axis, there are
parallel contacts between the vertical stems of “T”+“ ”
pairs. Hence, 4 packs in a manner that maximizes
fluorous contacts in every dimension.
Finally, CF3C6F11/toluene partition coefficients for 1-6
were carefully measured by GLC as described in the
Experimental Section. Data are summarized in Table
1. Interestingly, a small amount of 1 can reproducibly
be detected in the toluene phase. However, the higher
homologues 2 and 3 do not detectably partition into the
toluene phase. Importantly, integrations of solvent
impurity peaks indicate that amounts less than 0.3%
might not be detected. Other trends are analyzed below.
signals of the CH2 groups were assigned from the J CP
,
1J CH, and J CF values (Experimental Section) and shifted
downfield with increasing proximity to the Rf8 moiety.
3. Oth er Rea ction s or Ch a r a cter iza tion . As we
studied the preceding phosphines and their metal com-
plexes, decomposition products believed to be phosphine
oxides were sometimes observed. Accordingly, an au-
thentic sample was sought. As shown in Scheme 1, 1
was treated with H2O2, which is often used to convert
phosphines to phosphine oxides.24a Workup gave the
expected product OdP(CH2CH2Rf6)3 (6) in 88% yield as
an analytically pure white powder. Consistent with
literature precedent, the 31P NMR chemical shift was
downfield of that of 1 (δ 41.2 vs -25.5). The CH2 13C
NMR signals exhibited chemical shifts and J CF values
comparable to those of 1, but J CP values that were much
1
2
different (δ 19.3, d, J PC ) 68 Hz; 24.2, t, J CF ) 24 Hz).
We also sought methods for the reduction of fluorous
phosphine oxides. Following an established protocol,24b,25
6 and excess HSiCl3 were reacted at 48 °C. As shown in
Scheme 1, workup gave 1 in 85% yield. However, NMR
analysis of the crude product showed traces of PH(CH2-
Discu ssion
(24) (a) Bhattacharya, A. K.; Roy, N. K. The Chemistry of Organo-
phosphorus Compounds; Hartley, F. R., Ed.; Wiley & Sons: New York,
1992; Vol. 2, p 197. (b) Gilheany, D. G.; Mitchell, C. M. The Chemistry
of Organophosphorus Compounds; Hartley, F. R., Ed.; Wiley & Sons:
New York, 1990; Vol. 1, p 167.
There is now an extensive literature on fluorinated
phosphines.26 However, most examples feature perfluo-
(26) Schnabel, R. C.; Roddick, D. M. ACS Symp. Ser. 1994, 55, 421
and references therein.
(25) Symmes, C., J r.; Quin, L. D. J . Org. Chem. 1976, 41, 238.

6306 J . Org. Chem., Vol. 63, No. 18, 1998
Ta ble 1. P a r tition Coefficien ts (27 °C)a
Alvey et al.
increase from 98.8:1.2 to >99.7:<0.3. This illustrates the
applicability of the “like dissolves like” paradigm, and
the possibilities for rational design. The actual coef-
ficients for 2 and 3 may be higher, but the amounts
remaining in the organic phase are subject to detection
limits as described above.
analyte
CF3C6F11/toluene
P(CH2CH2Rf6)3 (1)
P(CH2CH2Rf8)3 (2)
P(CH2CH2Rf10)3 (3)
P(CH2CH2CH2Rf8)3 (4)
P(CH2CH2CH2CH2Rf8)3 (5)
OdP(CH2CH2Rf6)3 (6)
98.8:1.2b
>99.7:<0.3
>99.7:<0.3
98.8:1.2c
98.9:1.1d
However, it should be emphasized that the absolute
solubilities of 1-3 in CF3C6F11 progressively decrease.
We find similar phenomena with non-phosphorus-con-
taining fluorous compounds. Since the partition coef-
ficients or relative CF3C6F11/toluene solubilities increase
in the series 1-3, there must be an even steeper decrease
in toluene solubilities. Such solubility decreases are
common as molecules approach macromolecular limits.
Another noteworthy trend involves 2, 4, and 5. As the
(CH2)x spacer segment is lengthened, detectable quanti-
ties of the phosphine are again found in the nonfluorous
phase. These compounds also exhibit a marked ac-
companying increase of absolute solubilities in toluene.
Interestingly, the phosphine oxide 6 has a higher parti-
tion coefficient than the corresponding phosphine 1.
The partition coefficients of 1, 4, and 5 are sufficiently
high that they could be viewed as “immobilized” with
respect to many laboratory applications. However, they
would slowly leach under some conditions and not meet
the most rigorous industrial end-use criteria. In this
regard, we believe it is essential for researchers develop-
ing fluorous catalysts or reagents to report careful
partition coefficient measurements. As noted above,
fluorous attributes have been claimed for triarylphos-
phines in which each aryl group bears a single pony tail.11
However, arylphosphine substituents should, relative to
the alkyl substituents 1-3, significantly enhance organic
phase affinities.
>99.7:<0.3
a
Derived from the average of 3-11 GLC injections as described
in the Experimental Section. All ratios were confirmed by a second
b
independent determination (agreement to (0.1). 98.8(0.5):
1.2(0.5). c 98.8(0.4):1.2(0.4). 98.9(0.3):1.1(0.3).
d
roalkyl or perfluoroaryl substituents. Although some of
these may possess appreciable affinities for fluorous
media, they were usually prepared in conjunction with
programs directed at new highly π acidic ligands. As
such, they should be poor substitutes for the good donor
phosphines employed in most metal-catalyzed reactions.
Nonetheless, they may be useful as replacements for π
acidic carbon monoxide ligands, thus affording fluorous
derivatives of metal carbonyl catalysts.
To our knowledge, trialkylphosphines of the formula
P((CH2)x(CF2)7CF3)3 are unknown prior to this work.
Other syntheses of 1, or derivatives thereof, have been
described previously.9 The first preparation, reported in
1985 but often overlooked in citation lists and literature
surveys, utilized PCl3 and the fluorous iodozinc reagent
IZnCH2CH2Rf6.9a While our work was in progress, Knoch-
el found that the reaction of PCl3 with the dialkyl zinc
reagent Zn(CH2CH2Rf6)2 and then BH3‚SMe2 gives the
borane adduct 1‚BH3 in 75% yield.9b Finally, the reaction
of PCl3 with the Grignard reagent IMgCH2CH2Rf6 has
been reported to give 1 in 50% yield.9c
These routes avoid the hazards associated with PH3.14
On the other hand, the generation of the fluorous zinc
or Grignard reagents requires the iodide ICH2CH2Rf69 or
an organoborane derived from the alkene H2CdCHRf6.9b
Our procedures are more direct and superior from the
standpoint of atom economy. We also spent considerable
effort trying to prepare 4 and 5 from PCl3 and the
corresponding Grignard or alkyllithium reagents.10 How-
ever, success was limited.
In summary, we have developed convenient large scale
syntheses of a family of approximately isosteric fluorous
trialkylphosphines, P((CH2)x(CF2)yCF3)3, which feature
modulated electronic properties and fluorous phase af-
finities. Syntheses of additional types of fluorous phos-
phines, as well as further applications in catalysis, will
be reported soon.
Exp er im en ta l Section
Nolan has probed the steric and electronic properties
of 1 calorimetrically.27 Experiments with [Rh(CO)2Cl]2
show that 1 is a poorer donor than P(CH2CH3)3, and a
comparable donor to P(C6H5)(CH3)2. This indicates,
consistent with other data above, that the (CH2)2 spacers
do not completely insulate the phosphorus from the Rf6
groups. Experiments with (η5-C5R5)Ru(COD)(Cl) (R ) H,
CH3) suggest a cone angle of 130° ( 4°, close to that of
P(CH2CH3)3 (132°). We anticipate that 1-5 will be
comparable sterically, and that 1-3 will be comparable
electronically. However, as evidenced by the trend in air
sensitivity, 4 and 5 are progressively more electron
releasing.
Gen er a l. All reactions and workups were conducted under
inert atmospheres unless noted. Solvents were employed as
follows: CF3C6F11, CF3C6H5, CHCl3, distilled from P2O5; CH2-
Cl2, distilled from CaH2; toluene, hexanes, benzene, ether,
distilled from Na/benzophenone; pyridine, distilled from Na;
ethylene glycol, dried over MgSO4 (24 h); C6D6, CDCl3 (Cam-
bridge Isotope Laboratories), used as received. Reagents were
utilized as follows: PH3 (Scott Specialty Gases),14 used as
received; H2CdCH(CF2)5CF3, H2CdCH(CF2)7CF3, H2CdCH-
(CF2)9CF3 (Oakwood/Fluorochem), freeze-pump-thaw de-
gassed (5×); ICF2(CF2)6CF3 (PCR), used as received;
HOCH2(CF2)7CF3 (PCR), dried over MgSO4; Bu3SnCH2CHd
CH2, AIBN, VAZO, H2O2 (Aldrich), used as received; (CF3-
SO2)2O (Aldrich), distilled from P2O5; KI, dried over P2O5 (100
°C, drying pistol, 24 h); HSiCl3 (ROC/RIC), vacuum trans-
ferred. Silica gel (Merck, grade 9385, 230-400 mesh) was
dried under vacuum (3 × 10-3 mmHg, 180 °C, 24 h). Instru-
mental data and NMR spectra with resonance assignments
are provided as Supporting Information.
To our knowledge, only a few partition coefficients
involving organic compounds and fluorous and organic
phases have been measured.7,28 The data in Table 1
reveal high fluorous phase affinities and several con-
spicuous trends. First, as the lengths of the Rf segments
increase in the series 1-3, the partition coefficients
P (CH2CH2(CF 2)5CF 3)3 (1). A test tube (80 × 150 mm) was
charged with H2CdCH(CF2)5CF3 (6.902 g, 19.94 mmol), AIBN
(28) (a) Sole´-Violan, L.; Devallez, B.; Postel, M.; Riess, J . G. New J .
Chem. 1993, 17, 581. (b) Hughes, R. P.; Trujillo, H. A. Organometallics
1996, 15, 286.
(27) Li, C.; Nolan, S. P.; Horva´th, I. T. Organometallics 1998, 17,
452.

Additions of PH3 to Monosubstituted Alkenes
J . Org. Chem., Vol. 63, No. 18, 1998 6307
(0.302 g, 1.84 mmol, 9 mol %), and a Teflon stir bar and placed
in a tube-shaped stainless steel bomb (30 cm3 volume). The
bomb was sealed and connected to a PH3 tank. The assembly
was evacuated and filled with N2 (3×), and evacuated and
pressurized with PH3 (75 psi, ca. 6.3 mmol).14,29 The bomb
was partially immersed in an oil bath (80-85 °C), and the
contents were stirred. Every 4 h, the bomb was repressurized
from 45-60 psi to 75 psi (ca. 2 mmol). After 22 h, the bomb
was vented, purged with N2 (1 h), transferred into a glovebox,
and opened. An aliquot of the dark orange viscous oil was
dissolved in CF3C6F11. A 31P NMR spectrum showed a mixture
of PH3-n(CH2CH2(CF2)5CF3)n (Scheme 1).16b A 1H NMR spec-
trum showed traces of alkene. Then CF3C6H5 (5 mL), VAZO
(0.255 g, 1.04 mmol), and H2CdCH(CF2)5CF3 (1.00 g, 2.89
mmol) were added to the oil. The mixture was kept in a
Schlenk flask at 90 °C for 24 h, and darkened. The solvent
was removed by oil pump vacuum to give a white solid
suspended in orange liquid. Then CF3C6F11 (20 mL) and
toluene (20 mL) were added. The layers were separated.
Volatiles were removed from the CF3C6F11 layer by oil pump
vacuum. The light orange liquid was distilled (150 °C, 0.050
mmHg, bulb-to-bulb) to give 1 as a colorless liquid (6.12 g, 5.71
mmol, 75% based upon total alkene). Anal. Calcd for
P (CH2CH2(CF 2)9CF 3)3 (3). A bomb was charged with
H2CdCH(CF2)9CF3 (6.04 g, 11.1 mmol), AIBN (0.200 g, 1.22
mmol, 11 mol %), and PH3 (75 psi, ca. 6.5 mmol)14,29 in a
procedure analogous to that for 1. After 12 h, the bomb was
repressurized to 75 psi (ca 4.0 mmol). After an additional 12
h, the bomb was vented, purged, opened, and analyzed by 31P
NMR16d as before. Then CF3C6H5 (5 mL), VAZO (0.10 g, 0.41
mmol), and H2CdCH(CF2)9CF3 (0.262 g, 0.480 mmol) were
added. The mixture was kept in a Schlenk flask at 90 °C for
2 h. The solvent was removed by oil pump vacuum and the
residue continuously extracted with benzene in a Soxhlet
apparatus. After 24 h, 3 was collected from the thimble as a
white solid and dried by oil pump vacuum (4.05 g, 2.42 mmol,
63% based upon total alkene), mp 102-103 °C (capillary),
100.8 °C (DSC).30 Anal. Calcd for C36H12F63P: C, 25.84; H,
0.72. Found: C, 25.64; H, 0.78.
1H NMR (δ, CF3C6F11) 1.67 (m, 6H), 2.13 (m, 6H); 13C{1H}
NMR (δ, CF3C6F11, partial) 16.4 (m), 27.4 (m); 31P{1H} NMR
(δ, CF3C6F11) -25.5 (s). MS (EI, direct inlet probe, m/z >1224)
1672 (M+, 100), 1653 (M+ - F, 84), 1603 (M+ - CF3, 2), 1553
(M+ - CF2CF3, 4), 1503 (M+ - (CF2)2CF3, 7), 1453 (M+ - (CF2)3-
CF3, 7), 1403 (M+ - (CF2)4CF3, 7), 1353 (M+ - (CF2)5CF3, 5),
1303 (M+ - (CF2)6CF3, 3), 1253 (M+ - (CF2)7CF3, 2), 1203 (M+
- (CF2)8CF3, 6), 1153 (M+ - (CF2)9CF3, 10), 1139 (M+
-
C
24H12F39P: C, 26.87; H, 1.12. Found: C, 26.71; H, 1.10.
CH2(CF2)9CF3, 23), 1126 (M+ - (CH2)2(CF2)9CF3 + H, 15), 1125
(M+ - (CH2)2(CF2)9CF3, 3).
1H NMR (δ, CF3C6F11) 1.67 (m, 6H), 2.15 (m, 6H); 13C{1H}
1
NMR (δ, CF3C6F11, partial) 16.5 (d, J PC ) 16 Hz), 27.6 (dt,
2J PC ) 20 Hz, 2J CF ) 23 Hz); 31P{1H} NMR (δ, CF3C6F11) -25.5
(s). MS (EI, direct inlet probe, m/z >724) 1072 (M+, 100), 1053
(M+ - F, 70), 1003 (M+ - CF3, 2), 953 (M+ - CF2CF3, 2), 903
(M+ - (CF2)2CF3, 5), 853 (M+ - (CF2)3CF3, 4), 803 (M+ - (CF2)4-
CF3, 2), 753 (M+ - (CF2)5CF3, 1), 739 (M+ - CH2(CF2)5CF3,
15), 725 (M+ - (CH2)2(CF2)5CF3, 2).
OdP (CH2CH2(CF 2)5CF 3)3 (6). A 1 dram vial was charged
with 1 (0.773 g, 0.721 mmol), CF3C6H5 (2 mL), and aqueous
H2O2 (0.5 mL, 30% w/w, ca. 4 mmol). The mixture was shaken
vigorously (2 min) and allowed to settle (15 min). A 31P NMR
spectrum of the lower CF3C6H5 layer showed 6 and a byproduct
(δ 43.5, 53.1; 98:2). Water (2 mL) was added, and the layers
were separated (aerobic workup). The aqueous layer was
washed with CF3C6H5 (2 mL). The CF3C6H5 layers were
combined and dried over MgSO4. The solution was concen-
trated (ca. 0.5 mL) and stored at -20 °C. After 24 h, the
resulting white powder was collected by filtration and dried
by oil pump vacuum to give 6 (0.689 g, 0.633 mmol, 88%), mp
52-56 °C (capillary), 53.5 °C (DSC).30 Anal. Calcd for
P (CH2CH2(CF 2)7CF 3)3 (2). A bomb was charged with
H2CdCH(CF2)7CF3 (10.02 g, 22.46 mmol), AIBN (0.270 g, 1.64
mmol, 7 mol %), and PH3 (75 psi, ca. 5.9 mmol)14,29 in a
procedure analogous to that for 1. After 16 h, the bomb was
vented, purged, opened, and analyzed by 31P NMR16c as before.
Then CF3C6H5 (20 mL), VAZO (0.225 g, 0.921 mmol), and
H2CdCH(CF2)7CF3 (1.00 g, 2.24 mmol) were added. The
slightly yellow mixture was kept in a Schlenk flask at 90 °C
for 24 h. The solvent was removed by oil pump vacuum to
give a white solid. Then CF3C6F11 (20 mL) and toluene (20
mL) were added. The layers were separated. Volatiles were
removed from the CF3C6F11 layer by oil pump vacuum. The
light yellow solid was dissolved in CF3C6H5 (ca. 50 mL) and
toluene (ca. 40 mL) was added. The sample was cooled to -20
°C. A tan solid precipitated, which was collected by filtration,
distilled (175 °C, 5 × 10-5 mmHg, bulb-to-bulb), and dissolved
in CF3C6H5 (10 mL). The solution was filtered through a silica
gel column (2 × 10 cm), which was rinsed with CF3C6H5 (100
mL). The solvent was removed by oil pump vacuum to give 2
as a white solid (7.88 g, 5.74 mmol, 70% based upon total
alkene), mp 47-48 °C (capillary), 47.5 °C (DSC).30 Anal.
Calcd for C30H12F51P: C, 26.25; H, 0.88. Found: C, 26.28; H,
0.93.
C
24H12F39PO: C, 26.48; H, 1.11. Found: C, 26.61; H, 1.05.
1H NMR (δ, CF3C6F11) 2.13 (m, 6H), 2.45 (m, 6H); 13C{1H}
NMR (δ, CF3C6F11, partial) 19.3 (d, 1J PC ) 68 Hz), 24.2 (t, 2J CF
) 24 Hz, w1/2 ) 8 Hz, and J PC < 4 Hz); 31P{1H} NMR (δ,
2
CF3C6F11) 41.2 (s). MS (FAB, m/z) 1089 (M+ + 1, 100).
Red u ction of 6. A Schlenk flask was charged with 6 (0.452
g, 0.415 mmol), CF3C6H5 (5 mL), HSiCl3 (2.30 g, 17.0 mmol),
and N2 gas, sealed, and placed in a 48 °C oil bath. After 4 h,
a
31P NMR spectrum showed 6 to be 90% consumed. After an
additional 1 h, volatiles were removed by oil pump vacuum,
and CF3C6F11 (5 mL) and toluene (5 mL) were added to the
colorless oily residue. The layers were separated. The solvent
was removed from the CF3C6F11 layer by oil pump vacuum to
give a colorless oil (0.430 g) that was distilled (100 °C, 8 ×
10-5 mmHg, bulb-to-bulb) to give 0.383 g of a colorless liquid.
A
31P NMR spectrum showed a mixture of 1 (96%), 6 (1%),
PH(CH2CH2Rf6)2 (2%),16b and two unidentified species (δ 103.4,
29.2; 1%, 1%). The liquid was dissolved in CF3C6H5. The
solution was filtered through a silica gel plug (2 × 1 cm), which
was rinsed with CF3C6H5. The solvent was removed from the
filtrate by oil pump vacuum to give 1 as a colorless liquid
(0.377 g, 0.352 mmol, 85%, >97% purity by 31P NMR).
H2CdCHCH2(CF 2)7CF 3 (7).21 A Schlenk flask was charged
with ICF2(CF2)6CF3 (18.722 g, 34.291 mmol), Bu3SnCH2CHd
CH2 (17.0 mL, 54.8 mmol), and CH2Cl2 (20 mL). The solution
was photolyzed (Rayonet model RMA-400; R.P.R. 2537 Å
lamps). After 1 h, CH2Cl2 (20 mL) was added (aerobic workup).
The biphasic mixture was extracted with CF3C6F11 (2 × 10
mL). The solvent was removed from the extracts by rotary
evaporation and the residue distilled (77-80 °C, 20 mmHg)
to give 7 as a colorless liquid (12.825 g, 27.872 mmol, 81%).
Anal. Calcd for C11H5F17: C, 28.71; H, 1.10. Found: C, 28.71;
H, 1.16.
1H NMR (δ, CF3C6F11) 1.67 (m, 6H), 2.16 (m, 6H); 13C{1H}
1
NMR (δ, CF3C6F11, partial) 16.5 (d, J PC ) 17 Hz), 27.6 (dt,
2J PC ) 21 Hz, 2J CF ) 24 Hz); 31P{1H} NMR (δ, CF3C6F11) -25.4
(s). MS (EI, direct inlet probe, m/z >924) 1372 (M+, 100), 1353
(M+ - F, 70), 1303 (M+ - CF3, 2), 1253 (M+ - CF2CF3, 3),
1203 (M+ - (CF2)2CF3, 5), 1153 (M+ - (CF2)3CF3, 3), 1103 (M+
- (CF2)4CF3, 2), 1053 (M+ - (CF2)5CF3, 1), 1003 (M+ - (CF2)6-
CF3, 4), 953 (M+ - (CF2)7CF3, 6), 939 (M+ - CH2(CF2)7CF3,
15), 926 (M+ - (CH2)2(CF2)7CF3 + H, 9), 925 (M+ - (CH2)2(CF2)7-
CF3, 1).
(29) The approximate initial amount of PH3 was calculated as
follows. The alkene volume (6.90 g ÷ 1.52 g/mL ) 4.54 mL in the
preparation of 1) and the stirring bar volume (0.4 mL) were subtracted
from the autoclave volume (30 mL), and the difference utilized in the
inert gas equation, n ) PV/RT (T ) 298 K; 75 psi gauge reading ) 5.1
atm above ambient pressure, or 6.1 atm total).
(30) For the graphical method used to obtain the melting point, see
Cammenga, H. K.; Epple, M. Angew. Chem., Int. Ed. Engl. 1995, 34,
1171; Angew. Chem. 1995, 107, 1284.
3
1H NMR (δ, CDCl3) 5.81 (ddt, J HH ) 17, 11, 7 Hz), 5.35
3
3
3
(dm, J HH ) 11 Hz), 5.33 (dm, J HH ) 17 Hz), 2.85 (dtm, J HH
) 7 Hz, J HF ) 18 Hz); 13C NMR (δ, CDCl3, partial) 125.4 (d,
3

6308 J . Org. Chem., Vol. 63, No. 18, 1998
Alvey et al.
1
1
1J CH ) 158 Hz), 122.6 (t, J CH ) 160 Hz), 36.1 (td, J CH ) 130
tion. The residue was distilled (74-75 °C, 15 mmHg) to give
10 as an analytically impure colorless liquid (4.783 g, 10.09
mmol, 56%). Anal. Calcd for C12H7F17: C, 30.40; H, 1.49.
Found: C, 31.32; H, 1.61.
Hz, J CF ) 22 Hz); 19F NMR (δ, CDCl3) -81.5 (t, J FF ) 8 Hz,
CF3), -113.8 (pseudopentet, 2F), -122.4 (m, 6F), -123.3 (m,
2F), -123.6 (m, 2F), -126.8 (m, 2F). IR (cm-1, CHCl3) νCdC
1649 m.
2
1H NMR (δ, CDCl3) 5.90-5.76 (m, 1 H), 5.17-5.05 (m, 2
H), 2.42-2.33 (m, 2 H), 2.27-2.07 (m, 2 H); 13C NMR (δ, CDCl3,
P (CH2CH2CH2(CF 2)7CF 3)3 (4). A bomb was charged with
7 (5.021 g, 10.91 mmol), AIBN (0.183 g, 1.14 mmol, 10 mol
%), and PH3 (100 psi; pressure maintained throughout reac-
tion)14 in a procedure similar to that for 1. After 4 h, the bomb
was vented, purged, opened, and analyzed by 31P NMR16e as
before. Then VAZO (0.027 g, 0.11 mmol) and 7 (1.020 g, 2.217
mmol) were added. The mixture was stirred at 100 °C for 12
h and dissolved in CF3C6H5 (10 mL). The solution was filtered
through a silica gel column (2 × 6 cm), which was rinsed with
CF3C6H5 (60 mL). The filtrate was concentrated by oil pump
vacuum (20 mL) and cooled to 10 °C. A white powder formed,
which was collected on a frit. The filtrate was concentrated
to 10 mL and cooled to 10 °C. A second crop of white powder
formed, which was similarly collected, combined with the first,
and dried by oil pump vacuum to give 4 (4.544 g, 3.213 mmol,
73% based upon total alkene), mp 71.5-72.5 °C (capillary),
67.1 °C (DSC).30 Anal. Calcd for C33H18F51P: C, 28.02; H, 1.28.
Found: C, 28.16; H, 1.31.
1
1
partial) 135.7 (d, J CH ) 155 Hz), 116.5 (t, J CH ) 154 Hz),
30.7 (tt, 1J CH ) 129 Hz, 2J CF ) 22 Hz), 24.6 (tt, 1J CH ) 128 Hz,
3J CF ) 4 Hz); 19F NMR (δ, CDCl3) -81.5 (J FF ) 9 Hz, CF3),
-115.1 (pseudopentet, 2F), -122.3 (m, 2F), -122.5 (m, 4F),
-123.3 (m, 2F), -124.1 (m, 2F), -126.7 (m, 2F). IR (cm-1
neat) νCdC 1647 m.
,
P (CH2CH2CH2CH2(CF 2)7CF 3)3 (5). A bomb was charged
with 10 (5.017 g, 10.58 mmol), AIBN (0.175 g, 1.06 mmol, 10
mol %), and PH3 (100 psi)14 in a procedure analogous to that
for 4. After 4 h, the bomb was vented, purged, opened, and
analyzed by 31P NMR16a,f as before. Then VAZO (0.209 g, 0.855
mmol) and 10 (0.781 g, 1.65 mmol) were added. The mixture
was stirred at 100 °C for 12 h and dissolved in CF3C6H5 (10
mL). The solution was filtered through a silica gel column (2
× 6 cm), which was rinsed with CF3C6H5 (60 mL). The solvent
was removed from the filtrate by oil pump vacuum. The
residue was dissolved in toluene (50 mL), and the solution was
cooled to 10 °C. A white powder formed, which was collected
on a frit. The filtrate was concentrated to 10 mL and cooled
to 10 °C. A second crop of white powder formed, which was
similarly collected, combined with the first, and dried by oil
pump vacuum to give 5 (3.905 g, 2.681 mmol, 66% based upon
total alkene), mp 44.5-45.0 °C (capillary), 40.2 °C (DSC).30
Anal. Calcd for C36H24F51P: C, 29.69; H, 1.66. Found: C,
29.52; H, 1.66.
1H NMR (δ, CF3C6F11) 1.46-1.38 (m, 6H), 1.83-1.69 (m,
6H), 2.23-2.03 (m, 6H); 13C NMR (δ, CF3C6F11, partial) 32.4
1
2
3
(ttd, J CH ) 131 Hz, J CF ) 22 Hz, J CP ) 12 Hz), 27.3 (td,
1J CH ) 126 Hz, J CP ) 15 Hz), 17.1 (td, J CH ) 129 Hz, J CP
)
2
1
1
17 Hz); 31P{1H} NMR (δ, CF3C6F11) -34.8 (s).
CF 3SO2OCH2(CF 2)7CF 3 (8).22 A round-bottom flask was
charged with HOCH2(CF2)7CF3 (22.472 g, 49.927 mmol),
pyridine (4.80 mL, 59.3 mmol), and CHCl3 (100 mL) and placed
in a 0 °C bath. Then (CF3SO2)2O (10.0 mL, 59.4 mmol) was
added dropwise with stirring over 30 min. The bath was
removed. After 12 h, solvent was removed by rotary evapora-
tion (aerobic workup). The white residue was dissolved in
ether (250 mL). The solution was washed with cold water (100
mL) and dried over MgSO4. The solvent was removed under
vacuum (10 mmHg) to give 8 as a white powder (27.103 g,
46.556 mmol, 93%) mp 33.5 °C (DSC).30 Anal. Calcd for
1H NMR (δ, CF3C6F11) 2.08-1.96 (m, 6H), 1.74-1.69 (m,
6H), 1.55-1.45 (m, 6H), 1.39-1.33 (m, 6H); 13C NMR (δ,
CF3C6F11, partial) 30.9 (tt, 1J CH ) 129 Hz, 2J CF ) 22 Hz), 27.7,
1
2
25.9 (2 × td, J CH ) 125/125 Hz, J CP ) 15/16 Hz), 21.9 (td,
1J CH ) 129 Hz, J CP ) 11 Hz); 31P{1H} NMR (δ, CF3C6F11
)
1
-32.8 (s).
P a r tition Coefficien ts. The following procedure is rep-
resentative. A 1 dram vial was charged with 1 (0.0390 g,
0.0364 mmol), CF3C6F11 (2.000 ( 0.015 mL), and toluene (2.000
( 0.015 mL), capped with a mininert valve, vigorously shaken
(2 min), and immersed (cap-level) in a 35 °C bath. After 12 h,
the bath was removed. After 1 h (ambient temperature 24
°C), the vial was taken into a drybox (27 °C). After 1 h, 0.400
( 0.005 mL aliquots of each layer were added to stock solutions
of hexadecane in hexane (2.000 ( 0.015 mL, 0.00222 M; for 4
and 5, 0.0111 M eicosane in hexanes). GLC analysis showed
8.52 × 10-5 mmol and 7.11 × 10-3 mmol of 1 in the toluene
and CF3C6F11 aliquots, for a 98.8(0.5):1.2(0.5) ratio (Table 1;
3-11 injections averaged for each run). The total amount of
1 calculated from these data (0.0386 g or 0.0360 mmol using
a 2.000/0.400 volume multiplier) is in close agreement with
that utilized.
C
10H2F20O3S: C, 20.63; H, 0.35. Found: C, 20.86; H, 0.42.
1H NMR (δ, CDCl3) 4.82 (t, J HF ) 12 Hz); 13C (δ, CDCl3,
3
partial) 68.3 (tt, J CH ) 157 Hz, J CF ) 28 Hz); 19F (δ, CDCl3)
-74.5 (t, J FF ) 12 Hz, CF3), -81.3 (m, 2F), -120.2 (m, 2F),
-122.3 (m, 6F), -123.3 (m, 2F), -126.6 (m, 2F).
1
2
ICH2(CF 2)7CF 3 (9). A round-bottom flask was charged with
8 (27.103 g, 46.556 mmol), KI (15.495 g, 93.342 mmol), and
ethylene glycol (270 mL) and fitted with a condenser. The
mixture was refluxed for 12 h and cooled. Water was added
(270 mL; aerobic workup). The mixture was extracted with
ether (2 × 150 mL). The extracts were washed with aqueous
Na2S2O3 (100 mL, 0.10 M) and dried over MgSO4. The solvent
was removed under vacuum (10 mmHg) to give 9 as a white
powder (24.324 g, 43.437 mmol, 93%), mp 37.2 °C (DSC).30
Anal. Calcd for C9H2F17I: C, 19.30; H, 0.36. Found: C, 19.28;
H, 0.42.
Ack n ow led gm en t . We thank the NSF (CHE-
9401572) for support of this research, Mr. Lazslo Kiss
for some exploratory reactions, Professor A. Rheingold
(University of Delaware) for preliminary X-ray data, and
Dr. Istva´n Horva´th (Exxon Corporate Research) for
many helpful discussions.
1H NMR (δ, CDCl3) 3.64 (t, J HF ) 17 Hz); 13C NMR (δ,
3
1
2
CDCl3, partial) -4.1 (tt, J CH ) 151 Hz, J CF ) 26 Hz); 19F
NMR (δ, CDCl3) -81.3 (t, J FF ) 12 Hz, CF3), -107.4 (pseudo-
pentet, 2F), -121.9 (m, 2F), -122.2 (m, 2F), -122.3 (m, 4F),
-123.2 (m, 2F), -126.6 (m, 2F).
H2CdCHCH2CH2(CF 2)7CF 3 (10).23 A Schlenk flask was
charged with 9 (10.075 g, 17.991 mmol), Bu3SnCH2CHdCH2
(8.40 mL, 27.1 mmol), VAZO (0.4327 g, 1.771 mmol, 10 mol
%), and CF3C6H5 (50 mL) and fitted with a condenser. The
solution was refluxed for 6 h. The solvent was removed by
rotary evaporation, and CH2Cl2 (100 mL) was added. The
biphasic mixture was extracted with CF3C6F11 (2 × 20 mL).
The solvent was removed from the extracts by rotary evapora-
Su p p or tin g In for m a tion Ava ila ble: Instrumental data
and NMR spectra with resonance assignments (2 pages). This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
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J O980692Y