Syntheses, derivatives, solubility, and interfacial properties of 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: Potential building blocks for syntheses of amphiphatic macromolecules

Article abstract of DOI:10.1021/jo016166f

2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me₃Si)₂NH and toluenesulfonyl chloride (TsCl) to give mainly CH₃C(CH₂OSiMe₃)₃ (1), and CH₃C(CH₂OTs)3 (2), respectively. With allyl bromide, the products were CH₃C(CH₂OCH₂ CH=CH₂)₂(CH₂OH) (3) and CH₃C(CH₂OCH₂CH= CH₂)(CH₂OH)₂·H₂O (4). The reactions of 4 with perfluoroalkyl iodides (R_fI) were catalyzed by Cu(I)Cl to form 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: (R_fCH=CHCH₂OCH₂) C(Me)(CH₂OH)₂ [R_f = C₄F₉ (5), C₈F₁₇ (6), and (CF₂CF₂)₄OCF(CF₃)₂ (7)]. Reduction of 5 and 6 with hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium salt of 9 was reacted with allyl bromide or acetyl chloride to form (C₈F₁₇CH₂ CH₂CH₂OCH₂)C(Me) (CH₂OX)(CH₂OH)₂ [where X = CH₂CH=CH₂ (10) or C(O)CH₃ (12)] and (C₈F₁₇ CH₂CH₂CH₂ OCH₂)C(Me)(CH₂OX)₂ [where X = CH₂CH=CH₂ (11) or C(O)CH₃ (13)]. Reaction of tolenesulfonyl chloride with 7 gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium salt of 4 gave (4-CF₃C₆H₄ CH₂OCH₂)C(Me) (CH₂CH=CH₂)(CH₂OH)·H₂O (15). The compounds were characterized by NMR (¹H, ¹³C, ¹⁹F, ²⁹Si), GC-MS, and high-resolution MS or elemental analyses. UV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si(CH=CH₂)₄ in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It crystallized in the monoclinic space group P2₁/c, and unit cell dimensions were α = 24.966(2) A (α = 90°), b = 6.1371(6) A (β = 100.730(2)°), and c = 10.5669(10) A (γ = 90°).

Full text of DOI:10.1021/jo016166f

1
588
J . Org. Chem. 2002, 67, 1588-1594
Syn th eses, Der iva tives, Solu bility, a n d In ter fa cia l P r op er ties of
2
-Meth yl-2-p olyflu or oa lk en yloxym eth yl-1,3-p r op a n ed iols:
P oten tia l Bu ild in g Block s for Syn th eses of Am p h ip h a tic
Ma cr om olecu les†
Bamidele A. Omotowa, Matthew R. J udd, Brendan Twamley, and J ean’ne M. Shreeve*
Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343
jshreeve@uidaho.edu
Received October 1, 2001
2
-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me
chloride (TsCl) to give mainly CH C(CH OSiMe (1), and CH C(CH
allyl bromide, the products were CH C(CH OCH CHdCH (CH OH) (3) and CH
CH )(CH OH) ‚H O (4). The reactions of 4 with perfluoroalkyl iodides (R I) were catalyzed by
Cu(I)Cl to form 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: (R CHdCHCH OCH )-
C(Me)(CH OH) [R ) C (5), C 17 (6), and (CF CF OCF(CF (7)]. Reduction of 5 and 6 with
hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium
3
Si)
OTs)
2
NH and toluenesulfonyl
(2), respectively. With
C(CH OCH CHd
3
2
3
)
2
3
3
2
3
3
2
2
)
2
2
3
2
2
2
2
2
2
f
f
2
2
2
2
f
4
F
9
8
F
2
2
)
4
3 2
)
salt of 9 was reacted with allyl bromide or acetyl chloride to form (C
8
F
17CH
17CH
2
CH
CH
2
CH
CH
2
OCH )C(Me)(CH
2
OCH )C(Me)(CH
2
2
-
-
OX)(CH
OX) [where X ) CH
2
OH)
2
[where X ) CH
2
CHdCH
CHdCH
2
(10) or C(O)CH
3
(12)] and (C
8
F
2
2
2
2
2
2
2
3
(11) or C(O)CH (13)]. Reaction of tolenesulfonyl chloride with 7
gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium
salt of 4 gave (4-CF CH OCH )C(Me)(CH CHdCH )(CH OH)‚H O (15). The compounds were
3
C
6
H
4
1
2
13
2
2
2
2
2
19
29
characterized by NMR ( H, C, F, Si), GC-MS, and high-resolution MS or elemental analyses.
UV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and
n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si-
(
CHdCH
crystallized in the monoclinic space group P2
R ) 90°), b ) 6.1371(6) Å (â ) 100.730(2)°), and c ) 10.5669(10) Å (γ ) 90°).
2
)
4
in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It
1
/c, and unit cell dimensions were a ) 24.966(2) Å
(
In tr od u ction
Perfluorochemicals have unique properties and are
compounds containing sites that could improve their
solubility in organic solvents, perfluorochemicals, and
possibly aqueous media. Now, we have found A to be a
useful precursor to the 2-methyl-2-polyfluoroalkenyl-
oxymethyl-1,3-propanediols. Reactions of either one or
two OH groups in the polyfluoroalkyloxymethyl-1,3-
propanediols yielded a number of compounds containing
hydroxy, ester, allyl, and tosylate groups that influenced
their solubility and, perhaps, their possible use as agents
for interfacial transfer. Such derivatives could impact
markedly the perfluorocarbon surfactant field. Although,
typically lipophilic and immiscible with some organic
1
solvents. However, polyfluorinated compounds contain-
ing functional groups such as -OH, NH
2
, -COOH,
-
CHO, -COOR, CdO, etc. have increased solubility in
2
,3
water and other organic solvents. Many polyfluorinated
amphiphiles, with their unique properties and potential
for applications as surfactants, coatings, adhesives, and
3
drug delivery systems, are known. However, asymmetric
substitution of 2-(hydroxymethyl)-2-methyl-1,3-propanediol
A) will provide new routes to polyfluorinated compounds
4
the molecular structure of A was published, no fluori-
nated derivatives of this compound were reported. Hence,
we report the single-crystal X-ray structure of 2-methyl-
(
that can be starting materials in the synthesis of
polymers with amphiphatic properties. As far as we
know, there has been no previous use of A for this
purpose. Part of our recent effort has been the investiga-
tion of useful new routes to prepare highly fluorinated
2
-(1′,1′,2′,2′,3′,3′,4′,4′-nonafluoroheptyloxymethyl)-1,3-
propanediol, 8.
Resu lts a n d Discu ssion
Polyols are useful starting materials for the syntheses
of polyfunctional compounds. Typical polyols such as
pentaerythritol and glycerol have extensive hydrogen
*
To whom correspondence should be addressed. Fax: 208-885-9146.
Dedicated to Professor Dr. Dieter Naumann on the occasion of his
†
6
0th birthday.
1) Hudlick y´ , M., Pavlath, A. E., Eds.; In Chemistry of Organic
(
bonding networks that require high temperatures for
Fluorine Compounds II: A Critical Review; ACS Monograph 187;
American Chemical Society: Washington, DC, 1995; pp 985-988.
reaction to occur5 and make it difficult to control the
6
degree of substitution. Despite our efforts to direct the
(
2) (a) Yu, D.; Fr e´ chet, J . M. J . Polym. Mater. Sci. Eng. 1998, 633-
6
1
34. (b) Milco, L. A.; Tomalia, D. A. U.S. Patent 5731095, March 24,
998. (c) Cooper, A. I.; Londono, J . D.; Wignal. G.; McClain, J . B.;
(4) Eilerman, D.; Lippman, R.; Rudman, R. Acta Cryst. 1983, B39,
263-266.
(5) (a) Gordon, M.; Scantlebury, G. R. J . Chem. Soc. B 1967, 1, 1-13.
(b) Yoshida, O.; Nagai, S. (to Mitsubishi Gas Chem. Co., Ltd., J apan),
J P 2000044570, Feb. 15, 2000. (c) David, M. A.; Henry, G. S. In
Glycerol: A J ack of All Trades; The Chemistry Hall of Fame, York
University: 1996; and references therein.
Samulski, E. T.; Lin, J . S.; Dobrynin, A.; Rubinstein, M.; Burke, A. L.;
Fr e´ chet, J . M. J .; DeSimone, J . M. Nature 1997, 389, 368-370.
(3) (a) Surfactant Virtual Library. http://www.surfactants.net/s-
comp.htm (accessed Sept 2001). (b) Fr e´ chet, J . M. J . Science 1994, 263,
710. (c) Ungar, E. C. (to Imax Pharm. Corp.) U.S. Patent 6,028,066,
February 22, 2000.
1
1
0.1021/jo016166f CCC: $22.00 © 2002 American Chemical Society
Published on Web 02/01/2002

2
-Methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols
J . Org. Chem., Vol. 67, No. 5, 2002 1589
reaction on the basis of reactant stoichiometry, a variety
of products were formed at elevated temperatures.7
However, asymmetric substitution of the 2-(hydroxy-
methyl)-2-methyl-1,3-propanediol (A) and 2-(chloro-
8
methyl)-2-methyl-1,3-dichloropropane (B) appeared to be
possible via stepwise methodologies, thus making them
likely intermediates for syntheses of our target polyfunc-
tional compounds.
Compounds 3 and 4 were obtained from reaction of
allyl bromide and A. They were purified either by dis-
tillation or by column chromatography (silica gel). With
reduced hydrogen bonding in 4 (compared with A), the
OH groups were more reactive at lower temperatures,
especially with sodium hydride or pyridine.
Although B reacted with allyl alcohol to give the allyl-
substituted derivative,8 the probability existed that the
chloride atoms might be involved in undesired reactions
in subsequent steps required to prepare the polyfluoro-
alkenyloxymethyl derivatives. In principle, one of the
terminal hydrogen atoms in the allyl substituent of
a
CH
fluoroalkyl iodide, R
C(Me)(CH Cl)
-type compounds.9 However, use of CuCl
or Pd as part of the catalyst system in these procedures
makes the chlorides very vulnerable at typical reaction
temperatures.10 Since our goal was to synthesize com-
pounds that contained a polyfluoroalkyloxymethyl sub-
stituent and two other nonsimilar reactive sites, B was
not a viable reactant.
2
dCHCH
2
OCH
2
C(Me)(CH
2
Cl)
2
could react with a per-
f
I, to produce R
f
CHdCHCH OCH
2
2
-
,10
9
2
2
The CuCl/H
the reactions of 4 and R
CF CF OCF(CF ] to give the respective 2-methyl-2-
polyfluoroalkenyl-1,3-propanediols (R CHdCHCH OCH )-
C(Me)(CH OH) [R ) C (5), C 17 (6), and (CF CF
OCF(CF (7)] in high yields. They were purified either
NCH
CH
OH/t-BuOH system catalyzed
2
2
2
f
I [R
f
4 9 8
) C F , C F17, and
(
2
2
)
4
3 2
)
f
2
2
2
2
f
4
F
9
8
F
2
2 4
) -
3 2
)
by distillation under reduced pressure or by column
chromatography. Progress of these reactions was moni-
tored by NMR ( H and F) and GC-MS. The peak area
Given the stability of -OH groups in the presence of
9
the CuCl catalyst system and the opportunity for several
1
19
low-temperature reactions that could lead to controlled
substitution of R CHdCHCH OCH C(Me)(CH OH) -type
f 2 2 2 2
compounds provided by the alcohol sites, A was the
starting material of choice. It was reacted with a variety
ratio changed from 2:1 for signals at ∼5.88 and 6.43 ppm
2 2
assigned to CH and CH in CHdCH , respectively, in the
1
H NMR spectrum of 4 to 1:1 in the spectra of 5-7. The
3
J
H-H values of 14.88 (5), 15.25 (6), or 15.48 (7) Hz for
3 2
of reagents such as (Me Si) NH and tosyl chloride (TsCl).
the alkene proton signals appearing at 5.88 and 6.43 ppm
in the H NMR spectra of 5-7 indicate that they were
Metathesis reactions did not occur at lower temperatures.
Under these conditions, control of the number of substi-
tutions was more difficult, and only tris(trimethylsilyl-
oxymethyl)ethane (1) or tris(tosylatemethyl)ethane (2)
was obtained as the major product. It was also difficult
to control the degree of substitution in further reactions
of 1 and 2. For example, the reaction of 2 with sodium
iodide in acetone gave a mixture of mono-, di-, and triiodo
derivatives in low overall yields.
1
11a
19
isolated as the E-isomers.
for fluorine atoms of the ICF
Also, the F NMR signal
- moiety in R I [R ) C
], typically observed at ca.
2
3
f
f
4 9
F ,
C
8
F
17, and (CF
2
CF
2
)
4
OCF(CF
)
2
3
-
1
64 ppm, shifted to ca. -112 ppm (doublet with J H-F )
0.35 (5), 11.86 (6), or 12.41(7) Hz, respectively) in the
13
2
spectra of 5-7. The CF CHdCH signals in the C NMR
2
spectra of 5-7 were observed as triplets ( J C-F ) 24 Hz)
+
at about 117 ppm. The [M + 1] ions were observed in
the mass spectra of 5-7. Compounds 6 and 7 are low-
melting waxy solids, and 5 is crystalline.
(
6) Ameduri, B.; Boutevin, B.; Karam, L. J . Fluorine Chem. 1993,
5, 43-47.
2 4
7) Reaction of allyl bromide with pentaerythritol [C(CH OH) ]
6
(
produced a mixture of mono-, di-, and triallyl (in a ratio of 11:48:24
according to GC-MS) in the total crude yield of 1%. This result was
reproduced in several attempts involving varying ratios of reactants
and reaction temperatures and times.
(8) (a) M u¨ th, A.; Huttner, W. G.; Asam, A.; Zsolani, L.; Emmerrich,
Ch. J . Organomet. Chem. 1994, 468, 149-163. (b) Ellermann, J .; Veit,
A. J . Organomet. Chem. 1985, 290, 307-319. (c) Fukui, H.; Sawamoto,
M.; Higashimura, T. Macromolecules 1994, 27, 1297-1302. (d) Mi-
dollini, S.; Cecconi, F. J . Chem. Soc., Dalton Trans. 1973, 681-683.
(
e) Burk, M. J .; Harlow, R. L. Angew. Chem., Int. Ed. Engl. 1990, 29,
462-1464. (f) J acobi, A.; Huttner, G.; Winterhalter, U.; Cunkis, S.
Eur. J . Inorg. Chem. 1998, 675-692.
9) (a) Gaucheron, J .; Santaella, C.; Vierling, P. Bioconjugate Chem.
Because of the reduced effect of hydrogen bonding, the
hydroxy groups of 5-7 were more easily reacted than in
A. The respective metal alkoxides were formed in reac-
tions with sodium, potassium, sodium hydride, or potas-
sium hydride at room temperature. In our hands, it was
1
(
2
3
1
001, 12, 114-128. (b) Burton, D. J .; Kehoe, L. J . J . Org. Chem. 1971,
6, 2596-2599. (c) Burton, D. J .; Kehoe, L. J . J . Org. Chem. 1971, 35,
339-1342. (d) Asscher, M.; Vofsi, D. J . Chem. Soc. 1963, 1887-1896.
(
e) Asscher, M.; Vofsi, D. J . Chem. Soc. 1963, 3921-3927.
(10) (a) Elschenbroich, C.; Salzer, A. Organometallics: A Concise
(11) (a) Pavia, D. L.; Lampman, G. M.; Kriz, G. S. In Introduction
to Spectroscopy, 2nd ed.; Saunders College Publishing: 1996; pp 200-
205. (b) Dobrovolna, Z.; Cerveny, L. Collect. Czech. Chem. Comm. 1997,
62 (9), 1497-1502. (c) Anwer, M. K.; Sherman, D. B.; Roney, J . G.;
Spatola, A. F. J . Org. Chem. 1989, 54, 1284-1289. (d) Hanson, R. W.
J . Chem. Educ. 1997, 74, 430-431.
Introduction, 2nd ed.; VCH: Weinheim, Germany, 1992; p 419. (b)
J asperse, C. P.; Curron, D. P. J . Am. Chem. Soc. 1990, 112, 5601-
5
609. (c) Palladium catalyzes the coupling of aryl and alkenyl halides
with alkenes: Masters, C. In Homologous Transition-Metal Catalysis
A Gentle Art; Chapman and Hall: New York, 1981; pp 1-37.
-

1
590 J . Org. Chem., Vol. 67, No. 5, 2002
Omotowa et al.
impossible to reduce 5-7 by using ammonium formate
and Pd/C as an H -generator for similar hydrogenation
However, the somewhat deactivated ole-
2
reactions.1
1b-d
finic bonds in 5 and 6 were reduced via Pd/C-catalyzed
hydrogenation in methanol or ethyl acetate to give 8 and
9
. These were stable, colorless or light yellow, low-melting
solids. Because of the lower percentage of fluorine, it was
possible to isolate 8 as a crystalline solid.
of the desired product in high yields. This knowledge is
useful for exploring other hydroxy-protective groups for
selective reactions in our ongoing research. However, it
was of interest to report on the solubility properties of
Reactions of the sodium salt of 9 with allyl bromide
gave a mixture of 10 and 11; reaction with acetyl chloride
gave a mixture of 12 and 13. These products were
separated by chromatography (silica gel). Compounds
5
-15.
Solu bility Stu d ies. In addition to the synthetic chal-
lenge of synthesizing these amphiphatic compounds, we
were also interested in the possibility of using 5-15 to
develop new surfactants. The discovery of new surfac-
tants that can facilitate the dissolution of nonfluorinated
organic molecules in perfluorochemicals is still an active
research area,12 especially since they have assumed an
1
0-13 were stable, viscous, light yellow liquids.
1
3
increasing role in medical therapy. Therefore, the
solubilities of the 5-15 in different solvent media were
examined.
Compound A is readily soluble in water, but, not
unexpectedly, the substituted derivatives, 3 and 4, were
less soluble. The introduction of polyfluoroalkyl moieties
in 5-9 resulted in a considerable reduction in their
solubilities in water (assumed to be on the order of 1 ×
-4
1
0
M). They were insoluble in pentane, but were soluble
in toluene, 1,1,2-trichlorotrifluoroethane (Freon-113),
perfluorodecalin (C10 18), dichloromethane, and n-octanol.
F
Compounds 9, 12, 14, and 15 were soluble in pentane,
methylene chloride, toluene, perfluorodecalin, and Freon-
1
1
13. Their solubilities in n-octanol are reported in Table
. Compounds 11 and 13 that do not contain a hydroxy
group were very soluble in most organic solvents, includ-
ing hydrocarbons, such as pentane and hexane.
The high fluorine content (typically causing lipophi-
licity) and hydrogen-bonding possibilities (encouraging
hydrophilicity) impact the solubility of these compounds
in organic solvents. The dual-nature structures of 5-12,
6
With TsCl, at temperatures between -5 and 5 °C, 7
gave the monotosylate, 14, as the only new compound.
Disubstitution did not occur, which may arise from a
combination of low-temperature and steric effects. How-
ever, this was fortunate since the goal was to retain one
hydroxy group in the molecule.
1
4, and 15 would classify them as amphiphiles that could
2
,3,14,15
demonstrate interfacial activity.
The OH sites may
be useful for ligation and may facilitate the solubilization
of nonfluorinated compounds into perfluorochemicals in
which they are normally not soluble. Therefore, we
determined the extent of redistribution of 9, 12, 14, and
1
5 from n-octanol into perfluorodecalin by UV spectrom-
etry. The percent of these compounds that passed into
the perfluorodecalin phase are reported in Table 1. The
OH group in n-octanol forms hydrogen-bonding networks
(
12) (a) Lehmler, H. J .; Bummer, P. M.; J ay, M. J . CHEMTECH
999, 29, 7-13. (b) William, T. D.; J ay, M.; Lehmler, H.-J .; Clark, M.
E.; Stalker, D. J .; Bummer, P. M. J . Pharm. Sci. 1998, 87, 1585-1589.
1
(
13) (a) Lowe, K. C. J . Fluorine Chem. 2001, 109, 59-65 and
references therein. (b) Lowe, K. C. In Organofluorine Chemistry:
Principles and Commercial Applications; Banks, R. E., Smart, B. E.,
Tatlow, J . C., Eds.; Plenum Press; New York, 1994; Chapter 26, pp
Equimolar amounts of the sodium salt of 4 with
4
-(trifluoromethyl)benzyl bromide led to 15, which upon
5
55-577. (c) Leonard, R. C. Anaesth. Intens. Care 1998, 26, 11-21.
analysis was found to be the monohydrate.
(
14) (a) Dale, J .; Fredriksen, S. B. Acta Chem. Scand. 1992, 46, 278-
In the syntheses of 11, 12, 14, and 15, low percentages
of side products were often encountered. Mixtures of
dichloromethane/methanol were very useful as eluents
in column chromatography for separating pure samples
282. (b) Thorne, C. M.; Rawle, S. C.; Adams, G. A.; Cooper, S. R. Inorg.
Chem. 1986, 25, 3848-3850. (c) Cooper, S. R. (to ISIS Innovation, Ltd.,
UK) U.S. Patent 5621144, Apr 15, 1997.
(15) Richter, B.; de Wolf, E.; van Koten, G.; Deelman, B.-J . J . Org.
Chem. 2000, 65, 3885-3893.

2
-Methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols
J . Org. Chem., Vol. 67, No. 5, 2002 1591
Ta ble 1. Solu bility a n d P er cen t of 9, 12, 14, a n d 15
Extr a cted fr om n -Octa n ol in to P er flu or od eca lin
spectrometer. The UV spectroscopic studies were carried out
using quartz curvettes, and the data were analyzed using
usual software. Elemental analyses were performed com-
mercially.
solubility (g/L)a
% interfacial transferb
compound
in n-octanol
[PFc/oct]
3 2 3 3
Syn th eses. [CH C(CH OSiMe ) ] (1). This compound was
9
16.2
8.3
18.1
15.3
14.33
16.97
8.05
obtained by heating 12 g (100 mmol) of 2-(hydroxymethyl)-2-
methyl-1,3-propanediol and hexamethyldisilazane (16.2 g, 100
mmol) in 15 mL of toluene under anaerobic conditions at 80
1
1
1
2
4
5
15.73
°
C for 24 h. The title compound was obtained from fractional
a
Determined from a saturated solution at 25 °C. A correlation
distillation at 112 °C/1 mm. The yield was 33% on the basis of
of UV absorbance to concentration on the standard Beer-Lambert
1
the amount of alcohol starting material. NMR (CDCl
.05 (s, 27H, -CH ), 0.76 (s, 3H CCH ), 3.33 (s, 6H, CCH
C, δ -0.6, 16.2, 42.0, 64.2; Si, δ +17.7. MS [mass, species,
3
): H, δ
b
plot. From n-octanol into perfluorodecalin phase. Fc ) perfluo-
0
3
3
2
O-
rodecalin.
13
29
);
+
+
intensity (%)]: 321, (M - Me) , 1; 291, [M - 3(Me)] , 0.5; 191,
+
+
with the hydroxy functionality(ities) in 9, 12, 14, and 15.
Since bonding interactions with perfluorodecalin are
essentially nonexistent, there was minimal transfer into
the perfluorochemical phase.
In phenol, the hydroxy group can be used for hydrogen
bond interactions, the aromatic ring is electron with-
drawing and can interact with electron-rich functional-
ities by π-π interaction. This donor-acceptor electronic
property of phenol makes it possible for it to redistribute
between two immiscible organic solvents.12 Hence, it was
one of our choices for study of the interfacial activities of
[M - 2(Me
Si : C, 49.94; H, 10.62. Found: C, 49.71; H, 10.37.
C(CH OSO CH
] (2)14. This compound was
3 3
Si)] , 78; 73, (Me Si) , 100. Anal. Calcd. for
C
14
H
36
O
3
3
[CH
3
2
2
C
6
H
4
3 3
)
obtained by heating 12 g (100 mmol) of 2-(hydroxymethyl)-2-
methyl-1,3-propanediol and TsCl (19.05 g, 100 mmoL) in 35
mL of tetrahydrofuran (THF) under anaerobic conditions at
0 °C for 12 h. The title compound was obtained by crystal-
lizing the crude oily product from a 20:1 pentane/ethyl acetate
8
mixture. The yield was 21% on the basis of the amount of
1
alcohol starting material. NMR (CDCl
-CH C), 2.42 (s, 9H, -C CH
.29, 7.66 (dd, 12H, -C CH ); C, δ 17.1, 21.7, 39.4, 69.7,
3
): H, δ 0.85 (s, 3H,
3
6
H
4
3 3 2
), 3.82 (s, 6H, CH CCH O-),
1
3
7
1
5
O
9
6
H
4
3
27.9, 130.1, 131.8, 145.4. MS [mass, species, intensity (%)]:
9
, 12, 14, and 15 between octanol and perfluorodecalin.
+
+
81, (M - 1) , 26; 427, [M - O
2
SC
6
H
CH
4
CH
3
3
] , 14; 411, [M -
In the other choice, tetravinylsilane, the polyolefins are
electron rich and do not associate by hydrogen bonding,
and its interactions would be expected to be limited to
π-π associations. Hence, 9 (containing two hydroxy
groups), 12 (containing one hydroxy and one acetyl
group), 14 (containing one hydroxy, one alkene, and one
tosyl group), and 15 (containing one hydroxy and one
trifluorophenyl group) were selected to represent com-
pounds with different functional groups that will have
different strength of bonding associations with either
phenol or tetravinylsilane.
Both phenol and tetravinylsilane are insoluble in
perfluorodecalin. When dilute solutions of phenol or
tetravinylsilane in n-octanol were shaken thoroughly
with perfluorodecalin, the resultant extractions into the
latter were subsequently studied by UV and NMR
spectroscopy. Results indicated that very little or none
of the phenol or tetravinylsilane transferred into per-
fluorodecalin. However, in similar experiments, when the
n-octanol contained small amounts of 9, 12, 14, or 15,
the UV and 1H NMR spectra of the perfluorodecalin
phase showed that 9 and 15 facilitated the transfer of
fractions of dissolved phenol from the alcohol into per-
fluorodecalin (Figure 1). Similarly, transfers of fractions
of tetravinylsilane from n-octanol into perfluorodecalin
+
+
-
3
SC
1, [C
Syn th esis of 2-(Hyd r oxym eth yl)-2-m eth yl-1,3-bis(a l-
lyloxym et h yl)p r op a n e [CH C(CH OH )(CH OCH CH d
CH ) ] (3) a n d 2-(Allyloxym eth yl)-2-m eth yl-1,3-bis(h y-
6
H
4
CH
3
] , 16; 172, [HO
3
SC
6
H
4
] , 30; 154, Ts , 100,
+
6
H
4
CH
3
] , 94.
(
3
2
2
2
2
2
d r oxym et h yl)p r op a n e Mon oh yd r a t e [CH
(CH OCH CHdCH )]‚H O (4). 2-(Hydroxymethyl)-2-methyl-
,3-propanediol (A) (20.25 g, 135 mmol), allyl bromide (16.35
g, 135 mmol), potassium carbonate (20.80 g, 150 mmol), and
0 mL of acetone were placed in a two-necked 500 mL flask
3 2 2
C(CH OH ) -
2
2
2
2
1
2
connected via a condenser and a stopcock to a nitrogen gas
inlet. The mixture was held at reflux at 120 °C for 36 h. After
the mixture was cooled, 100 mL of toluene and 10 mL of water
were added to the mixture, and stirring was continued for
another 5 min. The phases were separated, and the organic
phase was washed twice with 5 mL portions of water. The
cloudy aqueous phase was mixed with 50 mL of toluene and
the aqueous phase removed azeotropically over a Dean and
Stark setup. The combined organic phases were filtered and
4
dried over MgSO . The crude filtrate consisted of the three
possible allyl substitution products. A fraction distilling at
115-118 °C/1 mm was confirmed by GC-MS as 4 (GC retention
time ) 7.99 min) and another distilling at 96-100 °C/1 mm
was identified as 3 (GC retention time ) 8.45 min) substituted
products. Pure 4 (19.70 g, 73% yield) and 3 (4 g, 11.85%, on
the basis of alcohol starting material) were obtained by column
chromatography (silica gel) using successive elutions with (a)
9
2
2 2 2 2
8:2 CH Cl /MeOH and (c) 95:5 CH Cl /MeOH mixtures. When
equiv of allyl bromide was reacted with 1 equiv of A in
(
Figure 2) were facilitated by 12 and 14. The amounts of
either phenol or tetravinylsilane that transferred into
perfluorodecalin were determined from standard Beer-
Lambert plots.
similar reactions, the yields were 55% 3 and 20% 4.
Analytical data for [CH C(CH OH)(CH OCH CHdCH ) ]
3
2
2
2
2
2
1
(3). NMR (CDCl
CHdCH ), 3.29 (d, 6H, CH
d, 2H, CH CHdCH ), 5.07 (dd, 1H, CH
3
): H, δ 0.73 (s, 3H, -CH
3
), 3.46 (d, 2H, -CH
2
-
2
3
CCH
2
O-), 3.87 (t, 2H, OH), 3.85
CHdCH ), 5.80 (m,
2 2
H, CH CHdCH ); C, δ 17.4, 40.7, 67.3, 72.9, 75.0, 116.7 and
(
2
2
3
2
2
Exp er im en ta l Section
1
2
1
1
+
34.6. MS [mass, species, intensity (%)]: 201, (M + 1) , 0.3;
Gen er a l. The solvents (THF and diethyl ether) were dried
with sodium and distilled over a purple solution of benzophe-
none. A standard Schlenk line system was used for carrying
+
+
85, (M - CH
3
) , 70; 41, (CH
2
dCHCH
2
) , 100. HRMS for
+
C
11
H
20
O
4
(M + 1) calcd 201.1491, found 201.1485.
1
13
13
out the reactions under dry nitrogen conditions. H, C or [ C-
Analytical data for [CH
3
C(CH
): H, δ 0.73 (s, 3H, -CH
), 3.29 (d, 6H, CH CCH O-), 3.87 (t, 2H, OH),
3.85 (d, 2H, CH CHdCH ), 5.07 (dd, 1H, CH CHdCH ), 5.80
(m, 2H, CH CHdCH ); C, δ 17.4, 40.7, 67.3, 72.9, 75.0, 116.7
and 134.6. MS [mass, species, intensity (%)]: 161, (M - OH) ,
2
OH)
2
(CH
2
OCH
2 2
CHdCH )]‚
1
9
29
1
1
{
F}], F, and Si{ H} NMR spectra were recorded in CDCl
3
H
2
O (4). NMR (CDCl
CHdCH
3
3
), 3.46 (d, 2H,
1
13
19
on a spectrometer operating at 200 ( H), 50 ( C), 188 ( F),
-CH
2
2
3
2
2
9
and 59 ( Si) MHz. Chemical shifts are reported in parts per
2
2
2
2
1
13
million relative to the appropriate standard, Me
4
Si for H and
2
2
1
3
19
+
C or CFCl
3
for F NMR spectra. Mass spectra (EI or CI) were
+ +
3 2 2
) , 70; 41, (CH dCHCH ) , 100. Anal. Calcd
obtained on an electron impact 70 eV spectrometer, and high-
resolution mass spectra were obtained using a suitable mass
0.3; 145, (M - CH
for C : C, 53.91; H, 10.18. Found: C, 53.99; H, 9.58.
8
18 4
H O

1
592 J . Org. Chem., Vol. 67, No. 5, 2002
Omotowa et al.
F igu r e 1. UV absorption curves for perfluorodecalin [(- - -): background] and solubilized phenol (-).
F igu r e 2. UV absorption curves for perfluorodecalin [(- - -): background] and solubilized tetravinylsilane (-). Inset: 29Si NMR
spectrum of tetravinylsilane in the perfluorodecalin phase.
Syn th esis of CH
3
C[CH
2
OCH
2
CHdCHR
f
][CH
2
OH]
CF
2
4
(d, 2H, -CH
2H, CH CCH
CH CH)CHC
(dt, 1H, CH CHdCHC
2
CHdCH
2 3 2
), 3.37 (s, 4H, CH CCH OH), 3.55 (s,
[
(
w h er e R ) C (5), C
f
4
F
9
8
F
17 (6), a n d (CF
3
)
2
CF OCF
2
2
)
3
2
OCH -), 2.77 (s, 2H, OH), 5.78 (td, 1H,
2
7)]. A mixture of 0.99 g (6.19 mmol) of 4, 4.22 g (7.74 mmol)
2
4 9
F , J H-H ) 14.88 Hz, J H-F ) 10.35 Hz), 6.38
3 13
3
3
of perfluorooctyl iodide, 0.40 g (4.04 mmol) of copper(I) chloride,
.2 mL (19.88 mmol) of ethanolamine, and 6.0 mL (65.57
mmol) of tert-butyl alcohol was placed in a 100 mL two-necked
flask connected with a reflux condenser and a nitrogen inlet
via a two-way stopcock. The mixture was stirred at reflux at
0 °C for 48 h. On cooling, it was poured into a separating
funnel that contain 50 mL of CH Cl and 20 of mL water. The
organic layer was separated and the aqueous phase washed
twice with 15 mL portions of CH Cl . The combined organic
2
8
F
17, J H-F ) 14.88 Hz);2 C, δ 17.3, 20.6,
1
40.8, 67.7, 69.8, 74.9, 104-118.6, 116.9 (t,
J
C-F ) 24 Hz),
136.7; 19F, δ -81.1 (CF
CF
CF
CF
CHdCH), -112.2 (CF
CF
CF
-
-
3
2
2
2
3
2
3
CF
2
CF
2
CHdCH, J H-F ) 10.35 Hz), -123.2 (CF
3
CF CF
2
2
2
CHdCH), -126.1 (CF
3
CF
2 2 2
CF CF CHdCH). GC retention
+
8
time: 8.4 min. MS (EI) [mass, species, intensity (%)]: 379, (M
+
+
2
2
+ 1), 14; 158, (M - C
4
F
9
H)
, 3 3
45; 74, [(CH ) COH] , 100. Rapid
fragmentation (related to dehydration) of this compound made
+
2
2
it difficult to record accurate mass for the M ion of 5. Hence,
phases were dried over magnesium sulfate and evaporated
under reduced pressure to yield the crude product. GC-MS
analysis indicated that the expected product, 6, was 74% of
the crude product that included two other products. Purifica-
tion of 6 was achieved by repeated column chromatography
HRMS was obtained for the trimethylsilyl derivative of the
two hydroxy groups, i.e., C
4 9 2 2 3 2
F CHdCHCH OCH C(CH )(CH -
+
OSiMe with expected m/z ) 522. The (M - 15) ion at m/z
3 2
)
) 507 was stable enough for determination of accurate mass
+
of this compound. HRMS for C17
507.1433, found 507.1433.
H
28
O
3
F
9
Si
2
(M - 15) calcd
(
silica gel), eluting successively with 99:1 and 95:5 mixtures
of CH Cl :CH OH. Compound 6 was a light yellow waxy solid
bp ) 140 °C/1 mm). Yield ) 2.5 g (70%).
Analytical data for CH C[CH OCH CHdCHC
): H, δ 0.84 (s, 3H, -CH ), 4.12 (d, 2H, -CH
), 3.49 (s, 4H, CH CCH OH), 3.57 (s, 2H, CH CCH
-), 2.15 (s, 2H, OH), 5.86 (td, 1H, CH CHdCHC
CHd
17, J H-H ) 15.25 Hz); C, δ 16.9, 40.9, 67.6, 69.6, 75.2,
2
2
3
Analytical data for CH
(CF ][CH OH] (7). Yield ) 82%. NMR (CDCl
(s, 3H, -CH ), 2.66 (s, 2H, OH), 3.48 (s, 2H, CH
), 3.65 (br, 4H, CH CCH OH), 4.13 (s, 2H, CH
5.89 (td, 1H, CH CH)CHC
12.41 Hz), 6.48 (d, 1H, CH CHdCHC
3
C[CH
2
OCH
2
CHdCH(CF CF OCF-
2
2 4
)
1
(
(
3
)
2
2
2
3
): H, δ 0.82
CCH OCH
CCH OCH
3
2
2
8
F
17][CH
2
OH]
2
-
-
3
3
2
2
-
2
1
6). NMR (CDCl
3
3
2
3
2
3
2
3
),
3
CHdCH
OCH
2
3
2
3
2
2
8
F
17
,
J
H-H ) 15.48 Hz,
J
H-F
)
3
2
2
8
F
17
,
2
8
F
17, J H-H ) 15.48 Hz);
3
3
13
J
H-H ) 15.25 Hz, J H-F ) 11.86 Hz), 6.42 (dt, 1H, CH
2
C, δ 16.9, 41.2, 67.8, 72.6, 75.9, 117.2 (t, J C-F ) 24 Hz), 138.8;
3
13
19
CHC
1
CF
CF
CF
CF
8
F
F, δ -81.1 ((CF
3
)
2
CFOCF
2
CF
2
CF
2
CF
2
CF
2
CF
2
CF
2 2
CF CHdCH),
2
19
3
02.3-122.2, 117.2 (t, J C-F ) 24 Hz), 138.8; F, δ -81.0 (CF
3
2
3
2
-
-
-
-
-112.2 ((CF CFOCF
3
)
2
2
CF CF
2
2
CF
2
CF
2
CF
2
CF
3
2
CF
2
CHdCH, J H-F
2
2
2
2
CF
CF
CF
CF
2
2
2
2
CF
CF
CF
CF
2
2
2
2
CF
CF
CF
CF
2
2
2
2
CF
CHdCH,
CF CF CF
2
CF
2
CF
2
CHdCH), -112.0 (CF
3
CF
2
CF
2
CF
) 12.41 Hz), -122.5, -122.8, -123.9 ((CF
)
2
)
2
)
2
CFOCF
CFOCF
CFOCF
2
2
2
CF
CF
CF
2
2
2
CF
CF
CF
2
2
2
-
-
-
3
J
2
H-F ) 11.86 Hz), -122.9 (CF
CF
CF
CF
2
2
2
CF
CF
CF
2
CF
CF
2
CF
CF
2
CF
CF
2
CHdCH), -125.8 ((CF
CHdCH), -145.7 ((CF
3
3
2
2
CHdCH), -126.3 (CF
3
CF
2
CF
2
CF
2
2
2
2
CHdCH). GC retention time: 9.9 min. MS
2 2 2 2
CF CF CF CHdCH). MS [mass, species, intensity (%)]:
+
+
+
[
CF
mass, species, intensity (%)]: 579, (M + 1), 0.3; 219, (CF
3
-
745 (M + 1), 100; 727 (M - OH) , 10; 709, [R
f
CHdCHCH
OCH C(CH
] *, 5; 527, [R
)CFOCF
OCH
CHdC] , 28; 129, [C(CH
2
-
+
+
+
+
2
CF
2
CF
2
) , 0.8; 169, (CF
3
CF
2
CF
2
) , 2.8; 119, (CF
3
CF
2
) , 5;
OCH
(dCH
2
C(CH
2
+
3
)(CHdCH
2
)] *; 696, [R
f
CHdCHCH
2
2
3
)-
+
+
+
2
5
3
7, [CH
2
CH(CH
3
)
2
] , 100. Anal. Calcd. for C16
H
15
O
3
F
17: C,
)] *, 8; 665, [R CHdCHCH
f
2
OCH
f
CHdCH-
+
3.23; H, 2.61; F, 55.85. Found: C, 33.15; H, 3.07; F, 54.63.
Analytical data for CH C[CH OCH CHdCHC ][CH OH]
5). Yield ) 43%. NMR (CDCl ), 4.07
): 1H, δ 0.79 (s, 3H, -CH
CH
7; 169, [(CF
9; 143, [C(CH
3
] *, 5; 441, [(CF
2
)
8
CHdCHCH
CF] , 10; 158, [CH C(CH
OH) CH OCH
3
], 6; 235, [(CF
3
2
] ,
+
+
3
2
2
4
F
9
2
2
3
)
2
3
2
OH) CH
2
2
2
CHdC] ,
+
(
3
3
2
2
2
2
2
OH)
2
CH
2
-

2
-Methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols
J . Org. Chem., Vol. 67, No. 5, 2002 1593
+
+
)+, 13;
OCHdC] , 12; 103, [CH
3
C(CH
, 48. Anal. Calcd for C19
.03. Found: C, 31.84; H, 2.57. HRMS for C19
2
OH)
2
(CH
2
)] , 15; 69, (CF
3
CF
CF
CH
2
2
CF
CF
2
2
CF
CF
2
2
CF
CH
2
CF
CH
2
CF
2
CH
2
CH
2
), -112.0 (CF
CF CF CF
CF CF CF
3
CF
CF
CF
2
CF
CF
CH
2
CF
CF
CH
2
CF
CF
2
). MS
2
2
-
-
5
2
1
7, CH
3
(CH
2
)
3
H
15
O
4
F
23: C, 30.66; H,
2
2
), -122.9 (CF
3
2
2
2
2
2
2
H
15
O
4
F
23 (M +
2
CH
2
), -126.3 (CF
3
CF
2
CF
2
CF
2
2
2
2
2
2
+
+
)
calcd 745.0681, found 745.0673. R
CF CF CF CF CF
Syn th esis of CH
w h er e R ) C (8) or C
obtained from reduction of 5 and 6 with H
of a suspension of 5% Pd/C in methanol or ethyl acetate.
Analytical data for CH C[CH OCH CH CH ][CH OH]
8). Yield ) 99.9%. NMR (CDCl ): H, δ 0.74 (s, 3H, -CH ),
.79 (br, 2H, C CH CH CH O), 2.07 (m, 2H, C CH CH
CH O), 3.42 (s, 2H, C CH CH CH O), 3.37 (s, 4H, CH CCH
OH), 3.57 (q, 2H, CH CCH OCH
f
) (CF
3
)
2
CFOCF
2
CF
2
-
[mass, species, intensity (%)]: 621, (M + 1) , 0.7; 563, (M -
+
+
CF
2
2
2
2
2
2
.
OCH
2
CHdCH
2
) , 2; 71, (CH
) , 45; 41, (CH CHdCH
(M + 1) calcd 621.1299, found 621.1299.
2 2 2 2 8
Analytical data for CH3C[CH OCH CH CH C F17][CH
2
OCH
2
+
CHdCH
) , 100. HRMS for C19
2
) , 55; 57, (OCH
2
-
17
+
3
C[CH
2
OCH
2
CH CH
2
2
R
f
][CH
2
OH]
2
CHdCH
2
2
2
H
22
O
3
F
+
[
f
4
F
9
8
F
17 (9)]. Compounds 8 and 9 were
gas in the presence
2
2-
OCH2
CHdCH
2 2
]
(11). Yield ) 18%, on the basis of the amount
H, δ 0.83 (s, 3H,
-CH ), 1.86 (m, 2H, CH CH C F ), 2.17 (m, 2H, CH C F17),
C
4
F
9
2
2
of alcohol starting material. NMR (CDCl ):
1
3
2
2
2
2
3
1
(
3
3
3
2
2
8
17
2
8
1
4
F
9
2
2
2
4
F
9
2
2
2
-
-
3 2 2 2 2 2 8 17
3.55 (s, 2H, CH CCH OH), 3.51 (s, 2H, CH OCH CH CH C F ),
3.33 (s, 2H, CH OCH CHdCH ), 3.93 (d, 2H, CH CHdCH ),
2 2 2 2 2
2
4
F
9
2
2
2
3
-), 3.29 (t, 2H, OH); 1 C, δ
3
13
3
2
2
5.85 (m, 1H, CH CHdCH ), 5.17 (t, 2H, CH CHdCH ); C, δ
2
2
2
2
1
9
1
7.3, 20.6, 27.8, 40.8, 67.7, 69.8, 74.9, 76.8, 104-118.6; F, δ
17.1, 20.6, 27.8, 40.7, 67.8, 69.2, 70.1, 76.0, 77.0, 116.6, 134.2;
-
81.1 (CF
CH ), -123.2 (CF
CF CH CH
intensity (%)]: 381, (M + 1) , 2; 363, (M - OH) , 2; 72 (CH
3
CF
2
CF
2
CF
CF
2
CH
CF
2
CH
2
), -112.2 (CF
3
CF
2
CF
2
CF
2
CH
2
-
-
19F, δ -81.0 (CF CF CF CF CF CF CF CF CH CH ), -112.0
3
2
2
2
2
2
2
2
2
2
2
3
2
2
CF
2
CH CH ), -126.1 (CF
2
2
3
CF
2
CF
2
(CF CF CF CF CF CF CF CF CH CH ), -122.9 (CF CF CF -
3
2
2
2
2
2
2
2
2
2
3
2
2
2
2
2
). GC retention time: 8.9 min. MS [mass, species,
CF CF CF CF CF CH CH ), -126.3 (CF CF CF CF CF CF -
2
2
2
2
2
2
2
3
2
2
2
2
2
+
+
+
2
-
-
2 2 2 2
CF CF CH CH ). MS [mass, species, intensity (%)]: 661, (M
+
+
+
+
+
3
OCH
2
+
CH
2
CH
2
) , 55; 57, (OCH
2
CHdCH
2
) , 100; 43, (CH
2
CH
2
+ 1) , 0.7; 591, (M - CF ) , 2; 169, (CF CF CF ) , 3; 71, (CH -
OCH CHdCH ) , 54; 57, (OCH CHdCH ) , 52; 41, (CH CHd
CH2)
found 661.1624.
Analytical data for CH
OCOCH
3
2
2
+
2
CH ) , 55. X-ray crystallographic data: crystal system, mon-
oclinic; space group, P2
3
+
2
2
2
2
2
/c; unit cell dimensions, a ) 24.966(2)
+
, 100. HRMS for C H26O3F17 (M + 1)
+
calcd 661.1611,
1
22
Å (R ) 90°), b ) 6.1371(6) Å (â ) 100.730(2)°), c ) 10.5669-
(
0
10) Å (γ ) 90°); F(000) ) 776; crystal size ) 0.26 × 0.10 ×
3
C[CH
2
OCH
2
CH
2
CH
2
3
C
8
F
17][CH
2
-
3
.05 mm ; R1 (all data) ) 0.1790, wR2 ) 0.1670. Selected bond
1
3
][CH
2
OH] (12). Yield ) 77%. NMR (CDCl
), 2.03 (s, 2H, CH C(O)OCH
OCH O(O)CCH
CH CH 17), 4.05 (s, 2H, CH
17), 1.86 (m, 2H, CH OCH CH CH
): H, δ 0.87
lengths (Å): F(1)-C(1) ) 1.311(6), O(1)-C(8) ) 1.419(5), C(1)-
(
s, 3H, -CCH
3
3
2
), 3.26 (s, 2H, CH
3
-
C(2) ) 1.534(7). Selected bond angles (deg): C(7)-O(1)-C(8)
CCH
2
OH), 3.46 (s, 2H, CH
OCH
2
2
3
), 2.69 (br, 1H,
)
111.8(3), C(3)-C(2)-C(1) ) 116.4(5), O(1)-C(7)-C(6) )
OH), 3.99 (s, 2H, CH
OCH CH CH
.12 (m, 2H, CH
7.9, 66.5, 69.9, 74.9, 171.5; F, δ -81.0 (CF
2
2
2
2
C
8
F
2
-
1
09.0(4).
2
2
2
C
8
F
2
13
2
2
2
C
8
F
17),
Analytical data for CH
3
C[CH
2
OCH
3
2
CH
2
CH
): H, δ 0.81 (s, 3H, -CH
O), 2.10 (m, 2H, C CH
CH CH O), 3.41 (s, 4H, CH CCH
OCH
2
C
8
F
17][CH
2
OH]
2
2
2
2 2 2 2 8
OCH CH CH C F17); C, δ 15.3, 17.0, 20.8,
1
(
9). Yield ) 99.9%. NMR (CDCl
.85 (m, 2H, C CH CH
CH O), 3.45 (s, 2H, C
OH), 3.60 (q, 2H, CH
3
),
19
3
CF
CF
2
CF
CF
2
CF
CF
2
CF
CF
2
-
-
1
8
F
17CH
2
2
2
8
F
17CH
2
2
-
-
CF
CH
126.3 (CF
2
CF
2
CF
), -122.9 (CF
CF CF CF
2
CH
2
CH
2
), -112.0 (CF
CF CF CF
CF CF CF
3
CF
CF
CF
2
CF
2
CF
2
2
2
2
2
2
8
F
17CH
2
2
2
2
3
2
2
CH
2
3
2
2
2
2
CF
2
CF
CH
2
CF
2 2 2
CH CH ),
1
3
3
CCH
2
-), 3.49 (t, 2H, OH); C, δ
-
3
2
2
2
2
2
2
2 2
CH
2
). MS [mass,
1
9
1
7.1, 20.6, 27.8, 40.7, 67.8, 70.1, 76.0, 77.0; F, δ -81.0 (CF
3
2
2
-
-
-
+
+
species, intensity (%)]: 623, (M + 1) , 0.4; 605, (M - OH) , 1;
CF
CF
CF
2
2
2
CF
CF
CH
2
CF
CF
CH
2
CF
CF
2
CF
CH
2
CF
CH
2
CF
), -122.9 (CF
CF CF CF
2
CH
2
CH
2
), -112.0 (CF
CF CF CF
CF CF CF
3
CF
2
CF
2
CF
CF
+
+
2 3
) , 25; 43, (CH -
7
2, (CH
2
OCH
2
CH
2
CH
2
) ; 57, (OCH
2
CHdCH
2
2
2
2
2
3
2
2
2
CF
2
CF
2
+
CO) , 100. Anal. Calcd for C18
Found: C, 35.25; H, 2.85.
19 4
H O F17: C, 34.73; H, 3.06.
2
2
), -126.3 (CF
3
2
2
2
2
2
2
CF
2
CH
2
CH
2
).
GC retention time: 10.1 min. MS [mass, species, intensity (%)]:
Analytical data for CH
OCOCH (13). Yield ) 8.5%, on the basis of the amount of
alcohol starting material. NMR (CDCl
CCH ), 2.02 (s, 2H, CH C(O)OCH ), 3.46 (s, 2H, CH
O)CCH ), 3.99 (s, 2H, CH OCH CH CH 17), 4.05 (s, 2H,
CH OCH CH CH 17), 1.86 (m, 2H, CH OCH CH CH
.12 (m, 2H, CH
7.9, 66.5, 69.9, 74.9, 171.5; F, δ -81.0 (CF
3 2 2 2 2 8 2
C[CH OCH CH CH C F17][CH -
+
+
+
3 3
) ] ,
5
81, (M + 1) , 0.3; 563, (M - OH) , 0.6; 71, [CH
2
C(CH
40. Anal. Calcd
17 3
H O F17: C, 33.12; H, 2.95; F, 55.66. Found: C, 32.26;
3 2
]
+
+
,
5
8; 56, [CH
2
C(CH
3
)
2
] , 100; 43, [CH
2
CH
2
CH
3
]
1
3
): H, δ 0.87 (s, 3H,
OCH O-
for C16
-
(
3
3
2
2
2
H, 2.63; F, 54.54.
Syn th esis of CH
3
2
2
2
2 8
C F
3
C[CH
2
OCH
CHdCH
CH 17][CH
(11), C(O)CH (13)]. The procedures for the
2
CH
2
CH
(10), C(O)CH
OX] [w h er e X )
2
C
8
F
17][CH
2
OX]-
2
2
2
2
C
8
F
2
3
2
2
2 8
C F17),
[
CH
a n d CH
CH CHdCH
2
OH] [w h er e X ) CH
2
2
3
(12)]
1
2
2
2 2 2 2 8
OCH CH CH C F17); C, δ 15.3, 17.0, 20.8,
3
C[CH OCH CH
2
2
2
2
C
8
F
2
2
1
9
3
CF
CF
2
CF
CF
2
CF
CF
2
CF
CF
2
-
-
2
2
3
CF
CH
126.3 (CF
2
CF
2
CF
), -122.9 (CF
CF CF CF
2
CH
2
CH
2
), -112.0 (CF
CF CF CF
CF CF CF
3
CF
CF
CF
2
CF
2
CF
2
2
2
2
2
syntheses and isolation of 10-13 were essentially the same.
A mixture of 4 g (25 mmol) of 9 and 25 mL of THF and
magnetic stir-bar were placed in a two-necked 250 mL flask
connected with a stopcock to a nitrogen/vacuum inlet valve.
Under anaerobic conditions, sodium hydride (0.6 g, 25 mmol)
and 30 mL of diethyl ether were placed in a second flask. The
suspension of sodium hydride was slowly transferred to the
stirring solution of 9 under nitrogen. After the mixture was
stirred for 2 h at room temperature, a solution of 2.2 g (28.03
mmol) of acetyl chloride in 20 mL of diethyl ether was added.
A reflux condenser was connected to the flask and the reaction
temperature raised to 40 °C. Aliquots were evaluated by GC-
MS to establish the progress of the reaction. After 4 h, both
2
CH
2
3
2
2
2
2
CF
2
CF
CH
2
CF
2 2 2
CH CH ),
-
3
2
2
2
2
2
2
2 2
CH
2
). MS [mass,
+
+
species, intensity (%)]: 665, (M + 1) , 0.5; 647, (M - OH) , 1;
+ +
2 2 2 2 2 2 3
2, (CH OCH CH CH ) ; 57, (OCH CHdCH ) , 25; 43, (CH -
7
+
+
CO) , 100. HRMS for C20
found 665: 1201.
Syn t h esis of CH
22 5
H O F17 (M + 1) calcd 665.1196,
3
C(CH
2
OH )(CH
2 2 6 4 3 2
OSO C H CH )[CH -
OCH CHdCH(CF CF
2
2
2
)
4
OCF (CF )
3 2
] (14). This compound
1
6
was prepared by a modification of the literature procedure. p-
Toluenesulfonyl chloride (0.21 g, 1.1 mmol) was added to 7 (1
g, mmol) in 10 mL of dry pyridine at -5 °C. The mixture was
agitated until the chloride dissolved. Stirring was continued
at 0 °C for an additional 2 h. The mixture was then carefully
treated with 0.1, 0.1, 0.1, 0.2, and 0.5 mL of water at not more
than 5 °C, with each addition spread over 5 min. Finally, 10
mL of water was then added at -5 °C. The toluenesulfonate
was extracted with diethyl ether. The ether solution was
washed with ice-cold dilute sulfuric acid, water, and sodium
bicarbonate solution. It was dried over sodium sulfate and
filtered and the solvent removed under reduced pressure. The
crude product (14) was a light yellow liquid and was purified
by elution from a silica gel column by using dichloromethane.
No evidence for the disulfonated product was found, and any
unreacted 7 was eventually washed down with methanol.
CH
3
C[CH
2
OCH
2
CH
2
CH
2
C
8
F
17][CH
CH
2
OCH
F
2
CHdCH
OCH
2
][CH
2
OH]
(
(
(
10) and CH
3
C[CH
2
OCH
2
CH
2
2
C
8
17][CH
2
2
CHdCH ]
2 2
11) were formed and separated by column chromatography
silica gel) by using 100% CH Cl , 98:2 CH Cl /MeOH, and
00% MeOH as eluents, in succession. The retention times for
0 and 11 from the GC-chromatogram were 10.1 and 11.5 min,
respectively.
Analytical data for CH
2
2
2
2
1
1
3
C[CH
2
OCH
2
CH
2
CH
2
C
8
F
17][CH
2
-
): 1H,
OCH
δ 0.80 (s, 3H, -CH
CH 17), 2.91 (s, 1H, CH
.54 (s, 2H, CH OCH CH
CHdCH ), 3.93 (d, 2H, CH
CH ), 5.17 (t, 2H, CH
2
CHdCH
2
][CH
2
OH] (10). Yield ) 56%. NMR (CDCl
3
3
), 1.86 (m, 2H, CH
2
CH
2
C
8
F
17), 2.17 (m, 2H,
OH), 3.61 (s, 2H, CH CCH OH),
CH 17), 3.37 (s, 2H, CH OCH
CHdCH ), 5.85 (m, 1H, CH CHd
); C, δ 17.1, 20.6, 27.8, 40.7,
2
C
8
F
2
3
2
3
2
2
2
2
C
8
F
2
2
-
2
2
2
2
1
3
2
2
CHdCH
2
(16) Weygand, C. In Preparative Organic Chemistry, 4th ed.;
Higetag, G., Martini, A., Eds.; Wiley: New York, 1972; pp 229-230.
1
9
6
3 2
7.8, 69.2, 70.1, 76.0, 77.0, 116.6, 134.2; F, δ -81.0 (CF CF -

1
594 J . Org. Chem., Vol. 67, No. 5, 2002
Omotowa et al.
Ta ble 2. Am ou n ts of P h en ol a n d Tetr a vin ylsila n e
Tr a n sfer r ed fr om n -Octa n ol in to P er flu or od eca lin
(ii) Deter m in a tion of P a r tition Coefficien t of th e Test
Com p ou n d s Betw een n -Octa n ol a n d P er flu or od eca lin .
The redistribution of each of these compounds from n-octanol
into perfluorodecalin, reported as PFc/oct in Table 1, was
determined as follows: 2.0 mL of perfluorodecalin was added
to a solution of a known concentration of the test compound
in 2.0 mL of n-octanol, and the mixture was shaken thoroughly
and allowed to settle and separate into two clear, colorless,
immiscible phases. The n-octanol phase (top layer) was the
carefully separated. The concentration of the compound that
remained in the n-octanol phase was determined from the
standard curve. These concentrations were used to calculate
mmols transferred from n-octanol
into perfluorodecalinb
compounds
MWa
phenol
0.0278
tetravinylsilane
9
580
623
898
336
1
1
1
2
4
5
0.0135
0.0125
0.0704
a
MW ) molecular weight. b Original solutions before adding
perfluorodecalin consisted of: 0.2 g (2.128 mmol) of phenol/2 mL
of n-octanol/0.07 g of test compound (9 or 15) or 0.15 g (1.101 mmol)
of tetravinylsilane/2 mL of n-octanol/0.07 g of test compound (12
or 14). See Experimental Section for method for determination of
amounts in interfacial transfer.
P
Fc/oct according to the following equation:
PFc/oct
)
(initial - final) concentration of compound in n-octanol
initial concentration of compound in n-octanol
×
100
Analytical data for CH
OCH CHdCH(CF CF
NMR (CDCl ): H, δ 0.84 [s, 3H, CCH
.39 (s, 3H, C CH ), 3.33 (s, 2H, CH
CH CCH OCH CHdCH), 3.99 (d, 2H, CH
CH), 4.03 (s, 2H, CH CCH OSO CH
CH CHdCH(CF CF OCF(CF
CH(CF CF OCF(CF
2.1, 73.7, 117.3, 128.0, 129.9, 132.7, 145.0, 158.7; F, δ -81.3
3
C(CH
OCF(CF
2
OH)(CH
] (14). Yield ) 0.95 g, 79%.
, 2.30 (s, 1H, CH OH),
OH), 3.46 (s, 2H,
CCH OCH CHd
), 5.73 [dt, 1H,
CHd
]; C, δ 16.6, 21.5, 40.9, 65.9, 69.5,
2 2 6 4 3 2
OSO C H CH )[CH -
2
2
2
)
4
3 2
)
(
iii) Solu biliza tion of P h en ol a n d Tetr a vin ylsila n e in
1
3
3
2
P er flu or od eca lin . The solubilization of phenol and tetravi-
nylsilane were evaluated as follows: 0.2 g of either phenol or
tetravinylsilane was added to a 0.07 g of a solution of 9, 11,
2
6
H
4
3
3
CCH
2
3
3
3
2
2
2
2
3
2
2 6 4
C H
1
4, or 15 in 2.0 mL of n-octanol and shaken thoroughly for a
2
2
2
)
3
4
3 2 2
) ], 6.28 [d, 2H, CH
minute. Perfluorodecalin (2 mL) was added to the homoge-
neous n-octanol solution and the final mixture shaken vigor-
ously for another 1-2 min. When the mixture was allowed to
settle, phase separation occurred. The NMR and UV spectra
of the perfluorodecalin phases in the different experiments
were recorded. Determinations of quantitative amounts of
phenol and tetravinylsilane solubilized in perfluorodecalin
were calculated as the difference between the initial and final
concentrations in n-octanol, and using the equation in section
ii above. The data are reported in Table 2.
1
3
2
2
)
4
)
2
1
9
7
(CF
3
CF
2
CF
2
CF
2
CF
2
CF
CHdCH), -122.5, -122. 8, -123.9 (CF
CF CF CHdCH), -125.8 (CF CF CF CF
2
CF
2
CF
2
CHdCH), -112.1 (CF
3
CF
2
CF
2
3
2
-
-
-
CF
CF
CF
2
2
2
CF
CF
CF
2
2
2
CF
CF
CF
2
2
2
CF
CF
CF
2
2
2
CF
CF
2
2
2
2
3
2
2
CHdCH). Anal. Calcd for C26
21 6
H O SF23: C,
3
4.74; H, 2.34. Found: C, 35.34; H, 1.95.
Syn t h esis of CH C[CH OCH CF
OCH CHdCH ]‚H O (15). A mixture of 0.5 g (3.13 mmoL) of
and 10 mL of freshly distilled diethyl ether and a magnetic
3
2
2
C
6
H
4
3 2 2
][CH OH ][CH -
2
2
2
4
stir bar were placed in a two-necked 50 mL flask connected
via a stopcock to a nitrogen/vacuum inlet valve. A suspension
of sodium hydride (0.075 g, 3.125 mmol) in 15 mL of diethyl
ether was made up in a second flask under nitrogen. This was
added to the stirring solution of 4 at 0 °C and slowly warmed
to 25 °C. A solution of 0.75 g (3.125 mmol) of 4-trifluorometh-
ylbenzyl bromide in 15 mL of THF was added to the mixture
at 25 °C. After the mixture was stirred at this temperature
for 1 h, the flask was equipped with a reflux condenser and
the mixture heated at 40 °C for 3 h. After the mixture was
cooled, the solvents were evaporated under reduced pressure.
GC-MS analysis showed that the crude product was a mixture
of unreacted 4 (6%), mono-(15) (80%), and dibenzyl compounds
Con clu sion
The syntheses of new multifunctional and highly
polyfluorinated compounds were achieved via high-yield-
ing multistep procedures. Some of the compounds will
be valuable starting materials in further syntheses and
applications. Our investigation of their solubility and
some of their interfacial properties revealed that they are
soluble in many organic solvents and in perfluorodecalin.
They were transferred from n-octanol into perfluorodeca-
lin, and they also facilitated the solubilization of phenol
and tetravinylsilane into the perfluorochemical via a
similar transfer from octanol. The results indicate that
the composition of the new compounds provides a useful
basis on which to develop new surfactants for applica-
tions in perfluorochemicals. Since perfluorochemicals are
gaining increasing significance as blood substitutes,
liquid ventillators, etc., we anticipate that this contribu-
tion will lead to development of new useful surfactants.
(5%), along with other side products. The benzylated com-
pounds were separated from 4 by extracting the evaporated
crude mixture with hexane. Compound 15 was obtained pure
by repeated column chromatography using pentane/hexane
mixtures. The GC retention time of 15 was 11.1 min. Analyti-
cal data for CH
CH ]‚H O (15). Yield ) 73%. NMR (CDCl
CCH ), 2.75 (br, 1H, OH), 2.75, 3.41 (, 2H, CH
H, CH CCH OCH CF ), 3.57 (s, 2H, CH OCH
.55 (s, 2H, CH CCH OCH CF ), 3.95 (td, 2H, CH
), 5.26 (dd, 2H, CH OCH CHdCH ), 5.80 (m, 1H, CH
CHdCH ), 7.37, 7.55 (dd, 4H, CH
3
C[CH
2
OCH
2
C
6
H
4
CF
3
][CH
2
OH][CH
3
2
OCH
): H, δ 0.88 (s, 3H,
OH), 3.48 (s,
CHdCH ),
OCH
2
CHd
1
2
2
3
2
2
4
3
2
2
C
6
H
4
3
2
2
2
C
6
H
4
3
2
2
-
-
Ack n ow led gm en t. The authors acknowledge the
support of the National Science Foundation (Grant
CHE-9720365) and the Petroleum Research Fund,
administered by the ACS. We are grateful to Dr. G.
Knerr for obtaining HRMS data and to Dr. Alexander
Blumenfeld for some high-resolution NMR data. We also
thank Professor Frank Cheng for assistance in UV
experiments.
3
2
2
CHdCH
OCH
2
2
2
2
2
1
3
2
2
2
C
6
H
4
CF
3
); C, δ 17.2,
4
0.7, 68.1, 69.2, 72.5, 74.7, 116.9, 125.3, 125.4, 127.4, 134.6;
1
9
+
F, δ -62.7. MS [mass, species, intensity (%)]: 319, (M + 1) ,
+
+
2
77, (M - CH
2
+
CHdCH
2
) , 2; 159, (M - CF
3
C
6
H
4
CH
2
)
or
+
(CF
3
C
6
H
4
CH
2
) , 100; 41, (CH
2
CHdCH
2
) , 40. Anal. Calcd for
C
16
H
23
O
4
F
3
: C, 57.13; H, 6.89. Found: C, 56.91; H, 6.69.
Solu tion Stu d ies. (i) Deter m in a tion of Solu bility of
Test Com p ou n d s. Four different concentrations were made
for each of 9, 11, 14, and 15 in n-octanol. Their UV absorbance
maxima at 213 (9), 232 (11), or 234 nm (14 and 15) were
plotted to obtain the Beer-Lambert standard curve for each
compound. Concentrations correlating the UV absorbancies (in
the standard curves) of saturated solutions of 9, 11, 14, and
Su p p or tin g In for m a tion Ava ila ble: Tables of data col-
lection parameters, atom coordinates, bond distances and
angles, anisotropic thermal parameters, hydrogen coordinates,
and intermolecular hydrogen bonding. This material is avail-
able free of charge via the Internet at http://pubs.acs.org.
1
5 were reported as their solubility in g/L (Table 1).
J O016166F