Solvent-free catalytic isomerization of perfluoroalkyl allyl ethers

Article abstract of DOI:10.1039/c3nj01300f

A convenient method for the bulk preparation of environmentally safe perfluoroalkyl propen-1-yl ethers via isomerization of primary allyl ethers is presented. Herein the solvent-free isomerization was carried out in the presence of two ruthenium(ii) complexes: the ruthenium-hydride [RuClH(CO)(PPh ₃)₃] and the second generation Grubb's type catalyst dichloro[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-2-ylidene] (thien-2-ylmethylidene)(PCy₃) ruthenium(ii) known as CatMETium-RF3. A variety of reaction parameters such as the catalyst loading, the use of a base and UV photoirradiation have been investigated. We found that the presence of Bu₃N is beneficial to both catalytic systems and although CatMETium-RF3 was shown to be more active than [RuClH(CO)(PPh₃)₃], the catalytic activity of the latter can also be sensibly improved by UV irradiation. Carrying out the isomerization reaction with 0.1 mol% of [RuClH(CO)(PPh₃)₃] under UV-irradiation led to a ca. 30% improvement of the conversion compared to the same reaction carried out under sunlight and to a 60% improvement when the reaction is carried out in the dark thus mimicking the conditions present in an autoclave.

Full text of DOI:10.1039/c3nj01300f

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Solvent-free catalytic isomerization of
perfluoroalkyl allyl ethers
Cite this: New J. Chem., 2014,
38, 641
Dario Lazzari,*a Maria Cristina Cassani,*b Marta Anna Brucka,b Gavino Solinasb and
Marisa Prettoa
A convenient method for the bulk preparation of environmentally safe perfluoroalkyl propen-1-yl ethers
via isomerization of primary allyl ethers is presented. Herein the solvent-free isomerization was carried
out in the presence of two ruthenium(II) complexes: the ruthenium-hydride [RuClH(CO)(PPh3)3] and the
second generation Grubb’s type catalyst dichloro[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-
2-ylidene](thien-2-ylmethylidene)(PCy3) ruthenium(II) known as CatMETium_RF3t. A variety of reaction
parameters such as the catalyst loading, the use of a base and UV photoirradiation have been
investigated. We found that the presence of Bu3N is beneficial to both catalytic systems and although
CatMETium_RF3t was shown to be more active than [RuClH(CO)(PPh3)3], the catalytic activity of the
latter can also be sensibly improved by UV irradiation. Carrying out the isomerization reaction with
0.1 mol% of [RuClH(CO)(PPh3)3] under UV-irradiation led to a ca. 30% improvement of the conversion
compared to the same reaction carried out under sunlight and to a 60% improvement when the
reaction is carried out in the dark thus mimicking the conditions present in an autoclave.
Received (in Porto Alegre, Brazil)
21st October 2013,
Accepted 15th November 2013
DOI: 10.1039/c3nj01300f
www.rsc.org/njc
of PFOA is considered to be the most detrimental aspect in the
use of C8-fluorinated chains: PFOA is persistent in the environ-
1. Introduction
The insertion of perfluorinated moieties within the structure of ment, ubiquitously present in surface waters, and subject to
more traditional organic compounds confers unique properties long-range transport. It accumulates in bio-organisms, espe-
that have been largely exploited in several application fields.1–5 cially in top predators. Furthermore PFOA is increasingly found
To mention just a few: pharmaceuticals and agrochemicals, in food items and in drinking water. PFOA’s intrinsic properties
material science, surfactant chemistry, heat transfer fluids, such as its persistency, its potential for bioaccumulation and its
additives for polymers as well as materials for lithium-ion toxicity suggest that PFOA is a promising candidate for being
batteries.6–12 In this respect the synthesis and characterization identified as a Substance of Very High Concern.13–16
of novel fluorinated building blocks containing suitable func-
In this framework the readily available perfluoroalkyl allyl
tional groups that can be easily transformed into a wide range ethers represent an important class of starting materials that can
of compounds represent an important industrial target; never- be easily converted into perfluoroalkyl propen-1-yl ether derivatives
theless the existing concern towards long perfluorinated alkyl via a versatile and convenient double-bond isomerization reaction.
chains owing to their bioaccumulation, toxicity and environ- These molecules are among the most reactive monomers in the
mental persistence is making more and more important the cationic photopolymerization and are increasingly being used in
availability of fluorinated building blocks with shorter per- resin production.17–19 Perfluoroalkyl allyl ethers able to satisfy all
fluorinated carbon chains.
these requirements are easily prepared from the corresponding
In the development of such a new range of environmentally alcohols and the production of the latter of the type RFCH2OH
safe building blocks the fluorinated carbon chain moiety RF where RF = C3F7 and C5F11 from the corresponding butanoyl and
cannot be longer than six carbon atoms. Materials satisfying hexanoyl fluoride via the electrochemical fluorination (ECF)
this requirement do not deliver, during service life, perfluoro- route20–23 is part of the core competence of Miteni S.p.A.24–26
octanoic acid (PFOA) via oxidative degradation. The formation
Allyl ethers are reluctant to undergo free radical, cationic
and anionic polymerization, thus they have only limited value
as monomers for the production of polymers. To the best of our
knowledge the allyl ethers either polymerize after being iso-
merized to propen-1-yl ethers or they do not react at all.27–29
The isomerization reaction of allyl ethers can be catalyzed
by transition metal complexes (Scheme 1) and represents an
a
`
Miteni S.p.A., Localita Colombara 91, 36070 Trissino, Vicenza, Italy.
E-mail: dario.lazzari@miteni.com; Fax: +39 0445499507; Tel: +39 0445499560
b Dipartimento di Chimica Industriale ‘‘Toso Montanari’’, Viale Risorgimento 4,
40136 Bologna, Italy. E-mail: maria.cassani@unibo.it; Fax: +39 0512093694;
Tel: +39 0512093700
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synthesis of 1 and similar mono- and diallyl ethers (RF = CF3,
C2F5, C6F13, C7F15, –(CF2)3–, –(CF2)4–, –(CF2)8–) was reported in
the past (often using less attractive synthetic procedures with
sodium or sodium hydride), the ethers 2, 3 and 4 have not been
previously reported.37–40 Additionally the use of NaOH as a base
presents the advantage of minimising the presence of allyl
hydroperoxides whose presence has detrimental effects on the
subsequent isomerization reaction.36 The products, isolated
after distillation as colourless liquids, were characterized by
1H, 13C, 19F NMR and GC-MS analyses; the purity of the
products, as determined by CG, was greater than 99%.
Scheme 1 Isomerization of alkyl allyl ethers catalyzed by transition metal
complexes.
example of an atom-economical process offering useful indus-
trial synthetic applications.30–32 Various low-valent ruthenium
complexes, particularly hydrides such as [RuClH(CO)(PPh3)3]
act as very efficient pre-catalysts for the homogeneously cata-
lyzed double-bond isomerization.33–36
2.2 Isomerization studies
In this paper we report the solvent-free isomerization of
a variety of primary perfluoroalkyl allyl ethers using the com-
mercially available hydride complex [RuClH(CO)(PPh3)3] and
the non-hydride, second generation Grubb’s type catalyst
dichloro[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dimethylimidazol-
2-ylidene](thien-2-ylmethylidene)(PCy3) ruthenium(II) known as
CatMETium_RF3t.
In our present study, the isomerization of the primary allyl
ethers 1–4 into the corresponding propen-1-yl derivatives 5–8
catalyzed by two commercially available ruthenium complexes
under different reaction conditions has been investigated
(Scheme 3).
We initiated our investigation by using the hydride ruthe-
nium complex [RuClH(CO)(PPh3)3], a well known efficient
catalyst for this kind of reaction.33–36 Based on previous reports
by Urbala et al.36 and with the aim of keeping the process as
simple and convenient as possible, all isomerizations were
carried out in air under solvent-free conditions either using a
2. Result and discussion
2.1 Synthesis of perfluoroalkyl allyl ethers
Two fluorinated alcohols namely 1H,1H-perfluorobutan-1-ol 30 mL screw-capped ampoule or a 300 mL Parr autoclave
(RF = C3F7), 1H,1H-perfluorohexan-1-ol (RF = C5F11) and diol equipped with a mechanical stirrer and a heating mantle.
1H,1H,8H,8H-perfluorooctane-1,8-diol were used as starting In Table 1, entries 1–14, the results regarding the terminal
materials to give the corresponding perfluoroalkyl allyl ethers olefins 1–3 are summarized whereas entries 15–19 concern
by reaction with allyl bromide (1–3), cis-1,4-dichloro-2-butene the findings relative to the internal olefins cis–trans-4; in all
(cis-4) and trans-1,4-dibromo-2-butene (trans-4) in the presence the examined cases the selectivity of the reaction was quanti-
of NaOH in a 300 mL Parr autoclave (Scheme 2).
tative and the reported conversions were measured after the
When both starting reagents are liquids, as for 1, 2 and reactions had come to a complete standstill. We found that
cis-4, a solvent-free protocol was employed and although the the ruthenium catalyst is insoluble in the perfluorinated ethers
Scheme 2 Reaction conditions for 1, 2, cis-4: autoclave, 80 1C, NaOH, 7 or 8 h, neat. Reaction conditions for 3 and trans-4: autoclave, 80 1C, NaOH,
7 h, THF. The reported yields are related to the distilled products.
642 | New J. Chem., 2014, 38, 641--649
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Scheme 3 Isomerization of perfluorinated allyl ethers catalyzed by ruthenium complexes.
Table 1 Isomerization reactions catalyzed by [Ru(H)(Cl)(CO)(PPh3)3]a,b
Entry Substrate Cat. (mol%) Time (h) Conv. (% NMR)
Propen-1-yl ether isomers are the only products of this
reaction; however, in keeping with what was reported by other
authors,33,41,42 we observed that the presence of a base such
as Bu3N (completely soluble in the reaction mixture and with
bp 180 1C) can have dramatic effects on the final conversion:
with a cat. loading of 0.1% mol only in the presence of
n-tributylamine the starting substrates 1, 2, 3 are quantitatively
converted in 1 h (entries 3, 7, 14) with turnover frequencies
1
2
3
4
5
6
7
8
1
1
1
1
2
2
2
2
2
2
2
2
3
3
0.5d
0.1
6
24
1
1
6
14
1
19
1
1
5
8
22
1
16
17
1
18
1
100
5
0.1 + 5Bu3N (0.5)
0.05 + 5Bu3N (0.25)
0.5
100g
75
100
85
0.1
0.1 + 5Bu3N (0.5)
0.1 + dark
100g
82
(TOF) of 1000 hꢀ1
.
9
0.1 + 5Bu3N (0.5) + dark
100g
89
When the isomerization reaction was performed in a flask
placed in a stainless steel autoclave, lower conversions were
constantly found (entry 12). Furthermore, due to the medium
viscosity (d = 1.3–1.5 g cmꢀ3), we found that monitoring the
reaction using the autoclave sample collection valve led to large
evaluation errors; therefore, in order to take samples of the
reaction mixture, the autoclave had to be opened each time.
With the aim of understanding the reasons behind the differ-
ences observed running the reactions in a screw-capped
ampoule and in an autoclave we came to the conclusion that
the presence or absence of light could play an important role.
10
11
12c
13
14
15
16
17
18
19
0.1 + hne
0.05 + 5Bu3N (0.25)
0.1
70h
42
0.2 f
92
0.2 + 5Bu3N (1.0)
0.5 + 5Bu3N (2.5)
5.0d
5.0 + 5Bu3N (25.0)
0.2 + 5Bu3N (1.0)
5.0 + 25Bu3N (25.0)
100g
0
trans-4
trans-4
trans-4
cis-4
cis-4
100
100
0
100
a
The selectivity of the reaction was quantitative; the conversion of the
starting allyl ether was measured after the reaction had come to a
b
complete standstill. Unless otherwise stated, the reactions were car-
ried out in air in a 30 mL screw-capped ampoule, 140 1C, neat. Therefore using substrate 2, which is prepared on a large scale
c
d
Reaction carried out in a 300 mL Parr autoclave, 140 1C, neat. With
inhouse by Miteni, as a model molecule we repeated the
isomerization reactions in aluminium-wrapped screw-capped
ampoules with a catalytic loading of 0.1 mol% of [RuHCl(CO)-
(PPh3)3]. The comparison between entries 6 (sunlight) and
8 (dark) and the conversion profiles reported in Fig. 1 showed
e
this mol% the cat. is not totally soluble in 1 at 140 1C. Reaction
f
carried out under UV-Vis irradiation. 0.1 mol% per double bond.
g
h
TON = 1000, TOF = 1000 hꢀ1
.
TON = 1400, TOF = 280 hꢀ1
.
at room temperature but, up to 0.1% mol, it is totally soluble that indeed the sunlight has a positive effect on the isomeriza-
at 140 1C in all the ethers examined in our study. Moreover tion rates.
we also observed that the results of the catalytic runs are
To the best of our knowledge we could not find similar
dramatically sensitive to impurities in the substrates, therefore, observations for ruthenium catalyzed O-allyl isomerization
if necessary, all the starting allyl ethers were further distilled reactions reported in the literature. This is probably due to
prior to use. The conversion of O-allyl groups to propen-1-yl the fact that it is not so common to compare the same reaction
derivatives as well as the ratios of the unseparated E and Z carried out using two completely different instruments
1
stereoisomers were determined from the analysis of H NMR although the photochemical properties of [RuClH(CO)(PPh3)3]
spectra of the crude mixtures on the basis of vicinal have been investigated in detail in the past.43 It has been
3J(HCQCH) coupling constants and confirmed by GC and reported that when [RuClH(CO)(PPh3)3] is irradiated at 366 nm
GC-MS analyses.
in a sealed vessel (like in our experiments) approximately equal
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Next we studied the catalytic activity in the isomerization
reactions of the complex depicted below: the second generation
Grubb’s type catalyst dichloro[1,3-bis-(2,4,6-trimethylphenyl)-
4,5-dimethylimidazol-2-ylidene](thien-2-ylmethylidene)(PCy3)
ruthenium(II) (known as CatMETium_RF3t) under a variety of
reaction conditions.
Fig. 1 Reaction profile of conversion vs. time for the isomerization of 2 in
the absence (’) or in the presence of sunlight (m) with a catalytic amount
of 0.1 mol% of [RuHCl(CO)(PPh3)3].
Table 2 Comparison of isomerization of 2a
This ruthenium complex was used among the many cata-
lysts available for the following reasons: (i) it is a robust
thermally stable catalyst, (ii) it is produced on a large scale,
(iii) there are no licence fees and it can be acquired as any other
row material. Additionally, previous attempts of isomerization
of perfluoroalkyl allyl ethers with the first generation Grubb’s
type complex [RuCl2(PCy3)2CHPh] have always led to poor
results with very low conversions (ca. 4%).
The catalyst CatMETium_RF3 (hereafter abbreviated as RF3)
has been employed in cross-metathesis (CM) and ring-closing
metathesis (RCM) reactions; however, as often found, the
ruthenium-hydride species, which are formed from the decom-
position of the ruthenium metathesis catalysts, also promote
isomerization to a significant extent.46–49 As the isomerization
reactions reported in literature never involved perfluorinated
substrates we have decided to study the behaviour of this
catalyst also in consideration of the fact that self-CM of
perfluorinated olefins does not occur.50–52
Entry
Conditions
Conv. (% NMR)a
1
2
3
Dark
Sunlight
UV lamp
30
60
89
a
Reaction conditions: 0.1 mol% [RuClH(CO)(PPh3)3], 30 mL screw-
capped ampoule, neat, 140 1C, 1 h.
amounts of [RuClH(PPh3)3] and [RuClH(CO)2(PPh3)2] are formed.
The two complexes have similar solubilities and the former has
been reported to be a very efficient catalyst for the isomerization
of olefins.31,44
In view of these findings and in order to confirm this
hypothesis the isomerization of 2 was carried out by irradiating
the screw-capped ampoule with a UV-lamp (see the Experi-
mental part for details) observing after 1 h a conversion of
89% (Table 1, entry 10 and Table 2, entry 3) with a ca. 30%
improvement compared to the reaction carried out under the
same conditions in the presence of sunlight and a 60% rise
compared to the isomerization run without light as in an
autoclave.
Prolonged irradiation of the sample did not lead to a further
increase of conversion; yet this new UV-irradiated isomeriza-
tion protocol is of considerable interest because it represents a
valid alternative to the use of an amine whose presence
complicates the purification process. Additionally at an indus-
trial level it is very interesting for Miteni S.p.A. whose main core
technology is represented by the use of photoreactors.45
With regard to the internal double bond isomerization
of cis- and trans-4, as expected,31 at low catalytic loadings
(0.1–0.5 mol%) the isomerization did not occur even in the
presence of n-tributylamine (Table 1, entries 15 and 18) and
catalytic loadings as high as 5 mol% together with the base are
necessary in order to have a complete conversion to the same
isomer 8 in a short time (Table 1, entries 17 and 19). As already
A set of catalytic entries have been carried out with the aim
of investigating the influence of the catalyst loading and reac-
tion set-up on the reaction output and the results are summar-
ized in Table 3. Preliminary screenings were carried out with
Table 3 Isomerization reactions catalyzed by CatMETium_RF3a,b
Entry
Substrate
Cat. (mol%)
Time (h)
Conv. (% NMR)
1
1
2
2
2
2
2
0.5
5.0
1.0
0.1
14
24
24
1
11
5
100
100
33
2c
3c
4
100d
86e
100 f
0
5
6
7
8
0.05
0.05 + Bu3N (0.25)
0.5
5.0
trans-4
trans-4
2
17
100
a
The selectivity of the reaction was quantitative; the conversion of
mentioned at the beginning of this paragraph it should be the starting allyl ether was measured after the reaction had come to
b
a complete standstill. Unless otherwise stated, the reactions were
pointed out that at this concentration the ruthenium catalyst is
only partially soluble in the perfluorinated ethers, thus the real
concentration in solution is lower than the nominal one.
c
carried out in air a 30 mL screw-capped ampoule, 140 1C, neat. Reac-
d
tion carried out in a flask under argon in CDCl3 at 65 1C. TON = 1000,
f
TOF = 1000 hꢀ1
.
e TON = 1720, TOF = 156 hꢀ1
.
TON = 2000, TOF = 156 hꢀ1
.
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two sets of signals characteristic of the E and Z 1-propenyl
groups in the ratio 33/67 whilst the GC analysis of the former
presented three peaks of similar integration for the Z,Z, E,E and
Z,E isomers with MS spectra only differing in the intensity
of the fragmentation peaks. When control experiments were
carried out in the absence of the ruthenium catalysts or in the
presence of only the amine, no isomerization reactions were
observed.
Propenyl ethers 5–8 are colourless liquid purified by distilla-
tion with isolated yields in the range 65–70% (see the Experi-
mental part), though the solvent-free conditions employed
for the synthesis make them suitable for direct use in the
cationic polymerization without the necessity of removing the
catalysts.53
Fig. 2 Isomerization of 2 in the presence of 0.05 mol% of RF3 (m) or with
0.05 mol% of [RuHCl(CO)(PPh3)3] with 0.25 mol% of n-tributylamine (’).
3. Conclusions
In this paper, the double bond isomerization of environmen-
tally compatible perfluoroalkyl allyl ethers to the corresponding
propen-1-yl ethers (E + Z isomers) catalyzed by two ruthenium(II)
complexes [RuClH(CO)(PPh3)3] and 2nd generation Grubbs’
catalyst CatMETium_RF3 has been studied under solvent-free
conditions. The latter, which has not been employed so far for
the isomerization of allyl systems, presented a significantly
higher efficiency in the studied reactions. In both cases the
presence of an HCl scavenger such as Bu3N led to a dramatic
improvement of the catalytic performances allowing 100%
conversions with low catalytic loadings (down to 0.05 mol%)
and short reaction times (1 h).
When the less expensive ruthenium hydride catalyst
[RuClH(CO)(PPh3)3] was used in the scale-up of the process in
autoclave for bulk preparations we found that the light plays an
important role in enhancing its catalytic activity and this
hypothesis has been confirmed by carrying out the reaction
under UV-lamp irradiation. The use of this new photoirradiated
isomerization protocol avoids the use of additional bases and is
of great interest for industries with technological competences
and facilities in the field of photoirradiated processes. Studies
concerning the polymerization of the prepared perfluoroalkyl
propen-1-yl ethers are underway.
the perfluoroalkyl allyl ether 2 in a round-bottom flask under
an argon atmosphere in CDCl3 at 65 1C. As shown in Table 3,
entry 2, under these experimental conditions with 5 mol% of
a Ru pre-catalyst the starting perfluorinated ether 2 was
totally converted to the corresponding propen-1-yl ether,
whereas we never identified products derived from a metath-
esis process. The catalyst loading reduction from 5 to 1 mol%
resulted in poorer conversion of the starting compound into its
isomer (Table 3, entry 3), with comparable regioselectivity
(vide infra). Afterwards we carried out the isomerization reac-
tion under the same experimental conditions described for
[RuClH(CO)(PPh3)3], namely under solvent-free conditions, in
air at 140 1C using a 30 mL screw-capped ampoule (Table 3,
entries 4–6). Similarly to [RuClH(CO)(PPh3)3], the catalyst RF3
is totally soluble in the perfluorinated substrates at 140 1C up
to 0.1 mol%.
As shown in Table 3, entry 4, with a 0.1 mol% catalyst
loading of RF3 the isomerization of 2 is complete in 1 h
whereas with [RuClH(CO)(PPh3)3], under the same conditions
(Table 1, entry 6), a maximum of 85% was obtained. The better
catalytic performance ensuing by the use of the Grubbs catalyst
is evident in Fig. 2 in which the conversion profiles of the two
catalysts were compared. In order to carry out the kinetic
studies within a 24 h period of time a catalytic loading of
0.05 mol% was chosen for both RF3 and [RuHCl(CO)(PPh3)3]
but for the latter the presence of 0.25 mol% n-tributylamine was
necessary.
4. Experimental section
4.1 General experimental procedures
The positive effect of the presence of Bu3N in the reaction The prepared derivatives were characterised by chromato-
mixture was also observed for RF3 (Table 3, entry 7) whereas, in graphic and spectroscopic methods. The NMR spectra were
accordance with the absence of CO ligands, no differences were recorded at 298 K using a Varian Gemini XL 300 (1H, 300.1; 13C,
observed by carrying out the reaction under photoirradiation. 75.5; 19F, 282.3 MHz) instrument; the deuterated solvents used
Finally for the isomerization of the internal olefin trans-4 even after being appropriately dried and degassed were stored in
with the more active RF3 a high catalyst loading is necessary in ampoules under argon on 4 Å molecular sieves; chemical shifts
order for the isomerization to occur.
were referenced internally to residual solvent peaks for 1H
In all entries reported in Tables 1–3, the double bond (CDCl3: 7.26 ppm) and 13C NMR (CDCl3: 77.00 ppm) spectra,
migration is not stereoselective and an E/Z ratio of ca. 40/60 and to CFCl3 (0.00 ppm) for 19F NMR spectra. Spectra have been
was found in all cases. The 1H and 13C NMR spectra of the edited using the software MestReNova Version: 8.0.2-11021, 2012
symmetric dipropen-1-yl ether 7 are identical to those of 6 with Mestrelab Research S.L.. Elemental analyses were performed on
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a ThermoQuest Flash 1112 Series EA Instrument. GC-MS ana- Y = 67%) was obtained by distillation as a colorless liquid (bp
lyses were performed using an Agilent 5973 instrument with a 142–145 1C, d = 1.49 g cmꢀ3). 1H NMR (300.1 MHz, CDCl3):
3
3
3
HP-5MS column (l = 30 m, I.D. = 0.25 mm, f.th = 0.25 mm); GC d 5.79 (ddt, Jtrans = 17.2 Hz, Jcis = 10.3 Hz, JH,H = 5.7 Hz, 1H,
analysis were performed using a Hewlett Packard HP-5890 CH2CHQCH2), 5.24 (ddt, 3Jtrans = 17.2 Hz, 2Jgem = 1.5 Hz, 4JH,H
=
=
3
2
instrument (split/splitless), single FID detector and autosam- 1.4 Hz, 1H, CH2CHQCH2), 5.18 (ddt, Jcis = 10.3 Hz, Jgem
pler with a 10 mL syringe. The yields were determined by GC 1.5 Hz, 4JH,H = 1.3 Hz, 1H, CH2CHQCH2), 4.05 (dt, 3JH,H = 5.67 Hz,
using decane (Fluka) as the internal standard and CH2Cl2 4JH,H = 1.2 Hz, 2H, CH2CHQCH2), 3.84 (tt, 3JH,F = 13.9 Hz, 4JH,F
=
(Merck) as diluent. Typical conditions were: temperature 1.5 Hz, 2H, CF2CH2). 13C NMR (75.5 MHz, CDCl3): d 133.1
program 40 1C for 2 min; 5 1C minꢀ1 to 120 1C ꢁ 0 min; (CH2CHQCH2), 118.5 (CH2CHQCH2), 119.4–107.3 (C5F11), 73.5
10 1C minꢀ1 to 240 1C per 20 min; He as gas carrier with a (CH2CHQCH2), 66.6 (t, JC,F = 25.7, CF2CH2). 19F NMR (282.3
2
3
constant flow.
MHz, CDCl3): d ꢀ81.76 (t, JF,F = 10.3 Hz, CF3), ꢀ120.25 (m, CF2),
The UV lamp irradiation was performed using a high- ꢀ123.68 (m, CF2), ꢀ124.23 (m, CF2), ꢀ127.01 (m, CF2). MS (EI), m/z
+
ꢃ
+
ꢃ
pressure, quartz sheathed mercury vapor lamp (Helios Ital- (rel. ab.%): 340 (M , 100), 313 ([M ꢀ CHQCH2] , 10), 71
+
+
ꢃ
ꢃ
quartz UV12F). The lamp functioned at 125 W and was ([M ꢀ C5F11] , 50), 41 ([CH2–CHQCH2] , 80). Anal. calcd (%)
equipped with a water-cooling system; the emission spectrum for C9H7F11O: C, 31.78; H, 2.07. Found: C, 31.74; H, 2.02%.
of the lamp provided by the manufacturer shows that several
emission lines are present in the UV region, the most intense of dodecafluorooctane (3). A flask was charged with a solution
which fall at ca. 315 and 365 nm. of 1H,1H,8H,8H-perfluorooctane-1,8-diol (25.00 g, 0.069 mol),
4.2.3 Synthesis of 1,8-bis(allyloxy)-2,2,3,3,4,4,5,5,6,6,7,7-
The liquid fluorinated alcohols 1H,1H-perfluorobutan-1-ol in THF (100 mL), allyl bromide (16.71 g, 0.138 mol) and ground
(RF = C3F7, bp = 96.97 1C, d = 1.60 g cmꢀ3 at 25 1C), NaOH (5.60 g, 0.140 mol) and placed in the autoclave. The
1H,1H-perfluorohexan-1-ol (RF = C5F11, bp = 128 1C, d = reaction was carried out for 7 h at 80 1C. The clean product 3
1.62 g cmꢀ3), where produced inhouse by Miteni S.p.A, (19.00 g, 0.043 mol, yield = 62%) was obtained by vacuum
via the ECF method; 1H,1H,8H,8H-perfluorooctane-1,8-diol distillation as a colorless liquid [bp 72–75 1C at 0.53 kPa
(mp = 80–83 1C) was purchased from Apollo Scientific; allyl (0.4 mmHg), d = 1.38 g cmꢀ3]. 1H NMR (300.1 MHz, CDCl3):
3
3
3
bromide, cis-1,4-dichloro-2-butene, trans-1,4-dibromo-2-butene, d 5.77 (ddt, Jtrans = 17.4 Hz, Jcis = 10.5 Hz, JH,H = 5.9 Hz, 1H,
n-tributylamine were purchased from Aldrich. The ruthenium CH2CHQCH2), 5.26 (ddt, 3Jtrans = 17.4 Hz, 2Jgem = 1.4 Hz, 4JH,H
=
=
3
2
catalysts [RuClH(CO)(PPh3)3] (Strem) and CatMETium_RF3 1.5 Hz, 1H, CH2CHQCH2), 5.20 (ddt, Jcis = 10.5 Hz, Jgem
(Degussa Evonik) were used as received.
1.3 Hz, 4JH,H = 1.3 Hz, 1H, CH2CHQCH2), 4.07 (dt, 3JH,H = 5.7 Hz,
4JH,H = 1.4 Hz, 2H, CH2CHQCH2), 3.86 (tt, 3JF,H = 14.3 Hz, 4JF,H
1.5 Hz, 2H, CF2CH2). 13C NMR (75.5 MHz, CDCl3): d 133.0
=
4.2 Synthesis of the perfluoroalkyl allyl ethers
The syntheses were always carried out in air in an autoclave (CH2CHQCH2), 118.2 (CH2CHQCH2), 119.1–107.7 (C6F12), 73.2
2
reactor (Parr Instrument series 4560, 300 mL) equipped with a (CH2CHQCH2), 66.8 (t, JC,F = 25.95, CF2CH2). 19F NMR (282.3
mechanical stirrer (0–1200 rpm) and a heating mantle (ꢂ1 1C). MHz, CDCl3): d ꢀ119.6 (m, CF2), ꢀ122.1 (m, CF2), ꢀ123.5
+
ꢃ
4.2.1 Synthesis of 4-(allyloxy)-1,1,1,2,2,3,3-heptafluorobutane (m, CF2). MS (EI), m/z (rel. ab.%): 442 (M , 15), 401
(1). A flask was charged with perfluorinated alcohol C3F7CH2OH ([M ꢀ CH2–CHQCH2]+, 100), 386 ([M ꢀ CHQCH–CH3–CH3]+,
(40.0 g, 0.20 mol), allyl bromide (24.2 g, 0.20 mol) and ground 40), 322 ([CF2H(CF2)4CH2OCH2CHQCH2]+, 75), 71 ([CH2OCH2–
NaOH (8.00 g, 0.20 mol) and placed in the autoclave. The CHQCH2]+, 30), 41 ([CH2–CHQCH2]+, 80). Anal. calcd (%) for
reaction was carried out for 7 h at 80 1C. The clean product 1 C14H14F12O2: C, 38.02; H, 3.19. Found: C, 38.06; H, 3.18%.
(33.6 g, 0.14 mol, Y = 69%) was obtained by fractional distilla-
4.2.4 Synthesis of 6,60-[(2Z)-but-2-ene-1,4-diylbis(oxy)]bis-
tion as a colorless liquid (bp 100–103 1C, d = 1.30 g cmꢀ3). (1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane) (cis-4). A flask was
1H NMR (300.1 MHz, CDCl3): d 5.88 (ddt, 3Jtrans = 17.1 Hz, 3Jcis
=
charged with perfluorinated alcohol C6H2F11OH (30.00 g,
3
10.3 Hz, JH,H = 5.7 Hz, 1H, CH2CHQCH2), 5.30 (m, 2H, 0.100 mol, d = 1.619 g cmꢀ3), cis-1,4-dichloro-2-butene (6.25 g,
3
CH2CHQCH2), 4.14 (d, JH,H = 5.7 Hz, 2H, CH2CHQCH2), 0.50 mol) and ground NaOH (4.00 g, 0.100 mol) and placed in the
3
3.91 (t, JH,F = 13.8 Hz, 2H, CF2CH2). 13C NMR (75.5 MHz, autoclave. The reaction was carried out for 8 h at 80 1C. The clean
CDCl3): d 133.0 (CH2CHQCH2), 118.7 (CH2CHQCH2), 120.5– product cis-4 (21.05 g, 0.032 mol, Y = 64%) was obtained by
105.5 (C3F7), 73.4 (CH2CHQCH2), 66.3 (t, 2JC,F = 25.8, CF2CH2). distillation under vacuum as a colorless liquid [bp 107–108 1C at
3
1
19F NMR (282.3 MHz, CDCl3): d ꢀ81.2 (t, JF,F = 9.5 Hz, CF3), 0.53 kPa (0.4 mmHg), d = 1.905 g cmꢀ3]. H NMR (300.1 MHz,
ꢀ120.7 (m, CF2), ꢀ127.9 (s, CF2). MS (EI), m/z (rel. ab.%): 240 CDCl3): d 5.78 (m, 2H, CHQ), 4.22 (m, 4H, CH2CHQ), 3.93
+
3
4
(M+ꢃ, 100), 69 (CF3 ꢃ, 40), 41 ([CH2–CHQCH2]+, 70). Anal. calcd (tt, JH,F = 13.8 Hz, JH,F = 1.5 Hz, 4H, CF2CH2); 13C NMR
(%) for C7H7F7O: C, 35.01; H, 2.94. Found: C, 35.00; H, 2.90%. (75.5 MHz, CDCl3):
d 129.1 (CHQ), 122.0–103.0 (C5F11),
2
4.2.2 Synthesis of 1,1,1,2,2,3,3-heptafluoro-4-[prop-1-en- 68.0 (QCHCH2O), 66.9 (t, JC,F = 25.5, CF2CH2). 19F NMR (282.3
3
1-yloxy]butane (2). A flask was charged with perfluorinated MHz, CDCl3): d ꢀ81.64 (t, JF,F = 10.6 Hz, CF3), ꢀ120.06 (m, CF2),
alcohol C6H2F11OH (140.3 g, 0.48 mol, d = 1.619 g cmꢀ3), allyl ꢀ123.45 (m, CF2), ꢀ124.08 (m, CF2), ꢀ126.89 (m, CF2). MS (EI), m/z
bromide (56.54 g, 0.48 mol) and ground NaOH (20.0 g, (rel. ab.%): 611 ([M ꢀ CH2–CHQCH2]+, 30), 353 ([M ꢀ C5F11CH2O]+,
0.50 mol) and placed in the autoclave. The reaction was carried 100), 339 ([M ꢀ C5F11CH2OCH2]+, 70), 69 ([CF3]+, 20). Anal. calcd (%)
out for 7 h at 80 1C. The clean product 2 (109.4 g, 0.32 mol, for C16H10F22O2: C, 29.46; H, 1.54. Found: C, 29.40; H, 1.50%.
646 | New J. Chem., 2014, 38, 641--649
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4.2.5 Synthesis of 6,60-[(2E)-but-2-ene-1,4-diylbis(oxy)]bis- (CHQCHCH3, cis), 120.4–108.6 (m, C3F7), 104.5 (CHQCHCH3,
2
(1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane) (trans-4).
A
flask cis), 101.8 (CHQCHCH3, trans), 68.1 (t, JC,F = 25.8, CF2CH2, cis),
was charged with perfluorinated alcohol C6H2F11OH (30.86 g, 65.7 (t, 2JC,F = 27.2, CF2CH2, trans), 11.9 (CH3, cis), 8.7 (CH3, trans).
0.103 mol, d = 1.619 g cmꢀ3), trans-1,4-dibromo-2-butene 19F NMR (282.3 MHz, CDCl3): d ꢀ81.5 (m, CF3), ꢀ121.5 (br s, CF2),
+
ꢃ
(10.00 g, 0.047 mol), ground NaOH (4.11 g, 0.103 mol) and ꢀ128.3 (s, CF2). MS (EI), m/z (rel. ab.%): 240 (M , 100), 119
+
+
ꢃ
+
ꢃ
THF (20 mL) and placed in the autoclave. The reaction was ([C2F5] , 24), 71 ([M ꢀ C3F7] , 80), 57 ([OCHQCHCH3] , 30), 41
+
ꢃ
carried out for 7 h at 80 1C. The clean product trans-4 (21.90 g, ([CHQCHCH3] , 90). Anal. calcd (%) for C7H7F7O: C, 35.01; H,
0.034 mol, Y = 72%) was obtained by distillation under vacuum 2.94. Found: C, 35.03; H, 2.93%.
as a colourless liquid [bp 116–118 1C at 0.53 kPa (0.4 mmHg),
1,1,1,2,2,3,3-Heptafluoro-4-[prop-1-en-1-yloxy]butane, (6), (mix-
1
d = 1.805 g cmꢀ3]. 1H NMR (300.1 MHz, CDCl3): d 5.83 (m, 2H, ture of Z and E isomers): Y = 67%, bp = 140–142 1C. H NMR
3
4
3
CHQ), 4.16 (m, 4H, CH2CHQ), 3.93 (tt, JH,F = 13.7 Hz, JH,F
=
(300.1 MHz, CDCl3): d 6.22 (d, Jtrans = 12.4 Hz, 1H,
1.5 Hz, 4H, CF2CH2); 13C NMR (75.5 MHz, CDCl3): d 128.8 CHQCHCH3), 5.94 (d, Jcis = 6.0 Hz, 1H, CHQCHCH3), 4.92
3
2
3
3
(CHQ), 122.5–103.5 (C5F11), 72.0 (QCHCH2O), 66.7 (t, JC,F
=
=
(dq, Jtrans = 12.4 Hz, JH,H = 6.8 Hz, 1H, CHQCHCH3), 4.56
(qd, 3JH,H = 6.8 Hz, 3Jcis = 6.0 Hz, 1H, CHQCHCH3), 4.18 (tt, 3JH,F
25.6, CF2CH2). 19F NMR (282.3 MHz, CDCl3): d ꢀ81.50 (t, 3JF,F
=
4
3
10.6 Hz, CF3), ꢀ120.06 (m, CF2), ꢀ123.45 (m, CF2), ꢀ124.04 13.2 Hz, JH,F = 1.5 Hz, 2H, CF2CH2), 4.10 (tt, JH,F = 13.2 Hz,
(m, CF2), ꢀ126.79 (m, CF2). MS (EI), m/z (rel. ab.%): 611 4JH,F = 1.5 Hz, 2H, CF2CH2), 1.59 (dd, JH,H = 6.8 Hz, JH,H
=
3
4
([M ꢀ CH2–CHQCH2]+, 30), 353 ([M ꢀ C5F11CH2O]+, 90), 339 1.6 Hz, 3H, CH3), 1.55 (dd, 3JH,H = 6.8 Hz, 4JH,H = 1.6 Hz, 3H, CH3).
([M ꢀ C5F11CH2OCH2]+, 100), 69 ([CF3]+, 10). Anal. calcd (%) for 13C NMR (75.5 MHz, CDCl3): d 145.3 (CHQCHCH3, trans), 144.7
C
16H10F22O2: C, 29.46; H, 1.54. Found: C, 29.49; H, 1.52%.
(CHQCHCH3, cis), 134.3–108.3 (C5F11), 104.4 (CHQCHCH3, cis),
2
101.7 (CHQCHCH3, cis), 68.2 (t, JC,F = 25.8, CF2CH2, cis), 65.9
(t, 2JC,F = 27.2, CF2CH2, trans), 11.8 (CH3, cis), 8.6 (CH3, trans). 19
F
4.3 Isomerization experiments
The perfluorinated allyl ethers were freshly distilled prior to NMR (282.3 MHz, CDCl3): d ꢀ82.23 (m, CF3), ꢀ120.60 (m, CF2),
use. The isomerization reactions with [RuClH(CO)(PPh3)] as the ꢀ123.87 (m, CF2), ꢀ124.45 (m, CF2), ꢀ127.25 (m, CF2). MS (EI),
pre-catalyst were carried out using the methods termed (b) and m/z (rel. ab.%): 340 (M+ꢃ, 100), 71 ([M ꢀ C5F11]+ꢃ, 70), 41
(c) (see Table 1); the isomerization reactions with CatME- ([CHQCHCH3]+ꢃ, 80). Anal. calcd (%) for C9H7F11O: C, 31.78;
Tium_RF3 as the pre-catalyst were carried out using the meth- H, 2.07. Found: C, 31.82; H, 2.05%.
ods termed (a) and (c) (see Table 3). The progress of the
2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-1,8-bis[prop-1-en-1-yloxy]-
1
isomerization was periodically monitored by H NMR and the octane (7) (mixture of all isomers): bp 78–80 1C at 0.53 kPa
clean products were obtained by fractional distillation. Repre- (0.4 mmHg). 1H NMR (300.1 MHz, CDCl3): d 6.22 (d, Jtrans
=
3
3
sentative reactions were reproduced to ensure outcome validity. 12.6 Hz, 1H, CHQCHCH3), 5.94 (d, Jcis = 6.0 Hz, 1H,
(a) In a round bottom flask in CDCl3 under argon with a CHQCHCH3), 4.93 (dq, Jtrans = 12.6 Hz, JH,H = 6.6 Hz, 1H,
magnetic stirrer.
3
3
3
3
CHQCHCH3), 4.56 (qd, Jcis = 6.0 Hz, JH,H = 6.6 Hz, 1H,
3
4
(b) The isomerization reactions in the scale of 3.00 g of allyl CHQCHCH3), 4.18 (tt, JH,F = 13.5 Hz, JH,F = 1.5 Hz, 2H,
3
4
substrate were performed in air under solvent-free conditions CF2CH2), 4.10 (tt, JH,F = 13.2 Hz, JH,F = 1.5 Hz, 2H, CF2CH2),
in 30 mL screw-capped ampoules with magnetic stirring in a 1.60 (dd, 3JH,H = 6.8 Hz, 4JH,H = 1.4 Hz, 3H, CH3), 1.57 (dd, 3JH,H
=
temperature-controlled (ꢂ0.1 1C) oil bath for a given period of 6.8 Hz, JH,H = 1.6 Hz, 3H, CH3). 13C NMR (75.5 MHz, CDCl3):
time. In a typical procedure (Table 1, entries 6, 8, 10) the screw- d 145.5 (CHQCHCH3, trans), 144.9 (CHQCHCH3, cis), 119.0–
capped ampoule was charged with 2 (3.00 g, 8.82 mmol) and 107.0 (C6F12), 104.4 (CHQCHCH3, cis), 101.7 (CHQCHCH3, cis),
4
2
2
[RuClH(CO)(PPh3)] (0.0084 g, 0.0088 mmol).
68.3 (t, JC,F = 26.0, CF2CH2, cis), 66.0 (t, JC,F = 26.3, CF2CH2,
(c) The isomerization reactions in the scale of 30.00 g were trans), 11.9 (CH3, cis), 8.8 (CH3, trans). 19F NMR (282.3 MHz,
carried out in air under solvent-free conditions in a flask placed CDCl3): d ꢀ120.40 (m, CF2), ꢀ122.30 (m, CF2), ꢀ123.70
in an autoclave reactor (Parr Instrument series 4560, 300 mL) (m, CF2). MS (EI), m/z (rel. ab.%): 442 (M+, 90), 401 ([M ꢀ
equipped with a mechanical stirrer (0–1200 rpm) and a heating CHQCH–CH3]+, 35), 386 ([M ꢀ CHQCH–CH3–CH3]+, 67), 322
mantle (ꢂ1 1C). In a typical procedure (Table 1, entry 12) a flask ([CF2H(CF2)4CH2OCHQCHCH3]+, 100), 71 ([CH2OCHQCH–CH3]+,
was charged with 2 (30.00 g, 88.2 mmol) and [RuClH(CO)(PPh3)] 40), 41 ([CHQCH–CH3]+, 70%). Calcd (%) for C14H14F12O2: C,
(0.084 g, 0.088 mmol) and placed in the autoclave.
38.02; H, 3.19. Found: C, 38.07; H, 3.20%.
1,1,1,2,2,3,3-Heptafluoro-4-[prop-1-en-1-yloxy]butane, (5), (mix-
6,60-[But-1-ene-1,4-diylbis(oxy)]bis(1,1,1,2,2,3,3,4,4,5,5-undeca-
ture of Z and E isomers): Y = 69%, bp = 52–54 1C. 1H NMR fluorohexane) (8), (mixture of Z and E isomers): bp 104–106 1C
3
1
(300.1 MHz, CDCl3):
d
6.22 (d, Jtrans
= 12.4 Hz, 1H, at 0.53 kPa (0.4 mmHg). H NMR (300.1 MHz, CDCl3): d 6.30
CHQCHCH3), 5.94 (d, Jcis = 5.9 Hz, 1H, CHQCHCH3), 4.93 (d, 3Jtrans = 12.6 Hz, 1H, CHQCHCH3), 6.01 (d, 3Jcis = 5.9 Hz, 1H,
3
3
3
3
3
(dq, Jtrans = 12.4 Hz, JH,H = 6.9 Hz, 1H, CHQCHCH3), 4.58 CHQCHCH3), 4.91 (dq, Jtrans = 12.7 Hz, JH,H = 7.5 Hz, 1H,
(qd, 3JH,H = 6.9 Hz, 3Jcis = 5.9 Hz, 1H, CHQCHCH3), 4.17 (tt, 3JH,F
=
CHQCHCH2), 4.58 (qd, Jcis = 6.2 Hz, JH,H = 7.3 Hz, 1H,
3
3
4
3
3
4
13.2 Hz, JH,F = 1.2 Hz, 2H, CF2CH2), 4.09 (tt, JH,F = 13.2 Hz, CHQCHCH2), 4.19 (tt, JH,F = 13.3 Hz, JH,F = 1.5 Hz, 2H,
4JH,F = 1.2 Hz, 2H, CF2CH2), 1.60 (dd, 3JH,H = 6.9 Hz, 4JH,H = 1.5 Hz, CF2CH2), 4.11 (tt, JH,F = 13.3 Hz, JH,F = 1.4 Hz, 2H, CF2CH2),
3H, CH3), 1.57 (dd, 3JH,H = 6.8 Hz, 4JH,H = 1.4 Hz, 3H, CH3). 13
3.92 (m, 2H, OCH2), 3.59 (m, 2H, OCH2), 2.40 (m, 2H,QCHCH2),
NMR (75.5 MHz, CDCl3): d 145.4 (CHQCHCH3, trans), 144.8 2.23 (m, 2H,QCHCH2). 13C NMR (75.5 MHz, CDCl3): d 146.6
3
4
C
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18 J. V. Crivello and S. S. Liu, J. Polym. Sci., Part A: Polym.
Chem., 1999, 37, 1199–1209.
19 R. Tripathy, J. V. Crivello and R. Faust, J. Polym. Sci., Part A:
Polym. Chem., 2013, 51, 305–317.
(CHQCHCH2, trans), 145.7 (CHQCHCH2, cis), 132.5–109.0
(C5F11), 105.0 (CHQCHCH2, cis), 102.4 (CHQCHCH2, trans),
2
73.1 (CH2), 72.1 (CH2), 68.4 (t, JC,F = 28.1, CF2CH2, cis), 67.5
2
(t, JC,F = 26.9, CF2CH2, trans), 27.6 (CH2, cis), 24.1 (CH2, trans).
19F NMR (282.3 MHz, CDCl3): d ꢀ81.15 (m CF3), ꢀ119.93
(m, CF2), ꢀ123.20 (m, CF2), ꢀ123.81 (m, CF2), ꢀ126.50 (m, CF2).
MS (EI), m/z (rel. ab.%): 652 (M+, 10), 353 ([M ꢀ C5F11CH2O]+, 80),
339 ([M ꢀ C5F11CH2OCH2]+, 100), 313 ([C5F11CH2OCH2]+, 30), 69
([CF3]+, 20). Anal. calcd (%) for C16H10F22O2: C, 29.46; H, 1.54.
Found: C, 29.50; H, 1.55%.
20 J. H. Simons, in Fluorine Chemistry, ed. J. H. Simons,
Academic Press, New York, 1950, vol. 1.
21 F. G. Drakesmith, Electrofluorination of Organic Compounds,
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1997, vol. 193.
22 J. H. Simons, J. Electrochem. Soc., 1949, 95, 47–59.
23 L. Conte and G. P. Gambaretto, J. Fluorine Chem., 2004, 125,
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24 Miteni S.p.A. (http://www.miteni.com) is part of I.C.I.G.
(International Chemical Investors Group, http://www.ic-
investors.com/) an industrial group composed by 21
chemical companies, operating worldwide in base chemicals,
fine chemicals, and polymers.
25 D. Lazzari, M. C. Cassani, M. Bertola, F. Casado Moreno and
D. Torrente, RSC Adv., 2013, 3, 15582–15584.
26 D. Lazzari, M. C. Cassani, G. Solinas and M. Pretto,
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Acknowledgements
M.C.C. wishes to thank the University of Bologna and the
`
Ministero dell’Universita e della Ricerca (MUR) (project: ‘‘New
strategies for the control of reactions: interactions of molecular
fragments with metallic sites in unconventional species’’, PRIN
2009) for financial support.
27 G. Odian, Principles of Polymerization, Wiley-Interscience,
New York, 4th edn, 2004.
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