α-(Difluoromethyl)styrene: Improved approach to grams scale synthesis

Article abstract of DOI:10.1016/j.jfluchem.2015.07.008

Improved, efficient, grams scale synthesis of α-(difluoromethyl)styrene (DFMST) based on nucleophilic difluoromethylation process using difluoromethylphenyl sulfone, is presented. Difluoromethylating agent (PhSO₂CF₂H) was obtained in two-step synthetic sequence with 69% overall yield. Three-step DFMST synthetic route was easily implemented for the preparation of gram quantities of the monomer, allowing for polymerization studies. The syntheses were based on the use of commercially available and reasonable in price starting materials and reagents.

Full text of DOI:10.1016/j.jfluchem.2015.07.008

Accepted Manuscript
Title: α-(Difluoromethyl)styrene: Improved Approach to
Grams Scale Synthesis
Author: Justyna Walkowiak-Kulikowska Joanna Kanigowska
Henryk Koroniak
PII:
S0022-1139(15)00208-0
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2015.07.008
FLUOR 8609
To appear in:
FLUOR
Received date:
Revised date:
Accepted date:
4-6-2015
3-7-2015
9-7-2015
Please cite this article as: J. Walkowiak-Kulikowska, J. Kanigowska,
H. Koroniak, rmalpha-(Difluoromethyl)styrene: Improved Approach
to Grams Scale Synthesis, Journal of Fluorine Chemistry (2015),
http://dx.doi.org/10.1016/j.jfluchem.2015.07.008
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*Graphical Abstract - Pictogram
α-(DIFLUOROMETHYL)STYRENE:
IMPROVED APPROACH TO LARGE-SCALE SYNTHESIS
Justyna Walkowiak-Kulikowska*, Joanna Kanigowska and Henryk Koroniak
Adam Mickiewicz University, Faculty of Chemistry, Umultowska 89b, 61-614 Poznań, Poland
*Corresponding author:
E-mail: Justyna.A.Walkowiak@amu.edu.pl
Dedicated to Professor Véronique Gouverneur on the occasion of receiving
the 2015 ACS Award for Creative Work in Fluorine Chemistry
Abstract
Page 1 of 17

*Graphical Abstract - Synopsis
α-(DIFLUOROMETHYL)STYRENE:
IMPROVED APPROACH TO LARGE-SCALE SYNTHESIS
Justyna Walkowiak-Kulikowska*, Joanna Kanigowska and Henryk Koroniak
Adam Mickiewicz University, Faculty of Chemistry, Umultowska 89b, 61-614 Poznań, Poland
*Corresponding author:
E-mail: Justyna.A.Walkowiak@amu.edu.pl
Dedicated to Professor Véronique Gouverneur on the occasion of receiving
the 2015 ACS Award for Creative Work in Fluorine Chemistry
Abstract
Improved, efficient, grams scale synthesis of α-(difluoromethyl)styrene (DFMST)
based on nuclephilic difluoromethylation process using difluoromethylphenyl sulfone,
is presented. Difluoromethylating agent (PhSO CF H) was obtained in two-step
2
2
synthetic sequence with 69% overall yield. Three-step DFMST synthetic route was
easily implemented for the preparation of gram quantities of the monomer, allowing
for polymerization studies. The syntheses are based on the use of commercially
available and reasonable in price starting materials and reagents.
Page 2 of 17

*Highlights (for review)
Highlights:

convenient three-step synthetic route towards non-commercially available
monomer




a key step in synthesis of DFMST was a nucleophilic difluoromethylation
efficient, easily scalable, two-step procedure to obtain difluoromethylating agent
the methods are easy to implement, selective and easily scalable
the syntheses are based on affordable, available from suppliers starting
materials
Page 3 of 17

*Manuscript
Click here to view linked References
α-(DIFLUOROMETHYL)STYRENE:
IMPROVED APPROACH TO GRAMS SCALE SYNTHESIS
Justyna Walkowiak-Kulikowska*, Joanna Kanigowska and Henryk Koroniak
Adam Mickiewicz University, Faculty of Chemistry, Umultowska 89b, 61-614 Poznań, Poland
*Corresponding author:
E-mail: Justyna.A.Walkowiak@amu.edu.pl
Dedicated to Professor Véronique Gouverneur on the occasion of receiving
the 2015 ACS Award for Creative Work in Fluorine Chemistry
Abstract
Improved, efficient, grams scale synthesis of α-(difluoromethyl)styrene (DFMST)
based on nuclephilic difluoromethylation process using difluoromethylphenyl sulfone,
is presented. Difluoromethylating agent (PhSO CF H) was obtained in two-step
2
2
synthetic sequence with 69% overall yield. Three-step DFMST synthetic route was
easily implemented for the preparation of gram quantities of the monomer, allowing
for polymerization studies. The syntheses were based on the use of commercially
available and reasonable in price starting materials and reagents.
Keywords: α-(difluoromethyl)styrene, nucleophilic fluoroalkylation, difluoromethyl-
phenyl sulfone, grams scale monomer synthesis, functional fluorinated polymers
1
. Introduction
Page 4 of 17

Fluorinated polymers exhibit range of very interesting properties, such as high
chemical and thermal stability, resistance to unfavorable weather conditions, low
refractive index, friction coefficient, dissipation factor, dielectric constant
at a simultaneously low water absorptivity. Hence, these high added value products
can find applications in many fields of advanced technology [1-5]. However, some of
them are not soluble in common solvent, others cannot be melted, or exhibit very
high melting points, which renders them difficult to process. Nevertheless, the
specific properties of fluoropolymers, in particular solubility as well as curability,
adhesion, surface properties, good hydrophilicity, heat and chemical resistance, can
be ensued by the nature of the functional groups in a lateral position of the copolymer
backbone. Additionally, introducing other fluorinated and nonfluorinated monomers
by co- and terpolymerization processes can result in formation of fluoropolymers
possessing interesting properties. Fluorinated aromatic polymers belong to
interesting subcategory of fluorinated polymers. Due to their desirable properties,
fluoroaromatic polymers may therefore have a potential use in the material science.
Our objective in the long run was to determine the influence of fluorine content in
the α-methylstyrenic monomers on reactivity, copolymer composition and thermal
stability of the resultant materials [6]. Therefore, it was necessary to develop an
efficient method to access gram quantities of α-difluoromethylstyrene (DFMST). The
difluoromethyl moiety has been widely used to modify physical, chemical and
biological properties of organic molecules. Although, several methods for the
synthesis of difluorometylated derivatives are available [7-13], only few protocols of
FMST synthesis on a large scale have been reported to date [14-16]. According to
the literature synthetic strategies the difluoromethyl α-substituted styrene was
prepared by two-step procedure, where a key step involved a nucleophilic addition of
Page 5 of 17

either Gringard’s reagent (phenylmagnesium bromide [14]) or organolithium
methyllithium [15]) to corresponding gem-difluorinated ketones. Subsequent
(
dehydration of the resultant difluoromethylated carbinol afforded desired α-
difluoromethylated styrene in good to very good overall yields. Previously, in
collaborative work an alternative strategy based on a nucleophilic difluoromethylation
process using the well-documented reagent difluoromethylphenyl sulfone, was
reported [16]. Herein, we wish to present an improved approach to the synthesis of α-
difluoromethylstyrene (DFMST) that can be obtained on a large scale through base
induced nucleophilic difluoromethylation (Scheme 1).
Scheme 1.
2
. Results and disscusion
2
.1. Difluoromethylphenylsulfone 3
Our initial survey focused on optimizing conditions for a synthesis of
difluormethylphenyl sulfone 3. This reagent can be prepared applying easily scalable
three-step literature protocol [17-19], albeit in moderate overall yield (44%, see
Supporting Info). Attempts to improve this synthetic route were not successful. We
therefore investigated an alternative strategy to obtain a desired nucleophilic difluoro-
methylating reagent 3 (Scheme 2, Table 1) [20,21].
Page 6 of 17

Scheme 2. Two-step synthesis of difluoromethylphenyl sulfone (3). Reagent and
conditions: First step: (1) PhSH (1, 1 equiv), Na (5 equiv)/MeOH, RT, 2 h; (2) CF ClH
2
(
2 equiv), -78 °C, 3 h; Second step: m-CPBA (4 equiv), CH Cl , 0~20 °C, 24 h.
2 2
The catalyst-free reaction of sodium thiophenolate generated in situ from thiophenol
and metallic sodium, with chlorodifluoromethane resulted in the formation of
difluoromethylphenyl sulfide 2 with 93% yield (lit. 63%) [20]. Subsequent oxidation of
was conducted at room temperature with excess of m-chloroperoxybenzoic acid
m-CPBA) in CH Cl and led to sulfone 3 which was isolated in 58% yield (lit. 58%)
1
2
(
2
2
[
21]. Studies aimed at probing the efficiency of this two-step synthetic sequence for
the preparation of larger scale quantities of difluoromethylating reagent (up to 40
mmol scale) indicated that overall yields for this route increased reasonably (from
5
4% up to 69%), although a slight yield decrease of the sulfide 2 synthesis was
observed (Table 1). Nevertheless, the two-step synthesis of difluoromethylphenyl
sulfone 3 was found to be easily scalable and 1.6 times more effective in comparison
with those already reported (69%, lit. 44%) [16].
Table 1. Synthesis of difluoromethylating agent 3
Difluoromethylphenyl Difluoromethylphenyl
b
Entry
Thiophenol
Yield
sulfide
sulfone
3 (58%)
3 (58%)
3 (88%)
a
a
a
a
a
a
1
2
1 (4.00 mmol)
1 (16.0 mmol)
2 (93%)
2 (81%)
2 (78%)
54%
47%
69%
3
1 (40.0 mmol)
a
b
Isolated yield; Isolated overall yield over two steps.
2
.2. α-(Difluoromethyl)styrene 7
Page 7 of 17

The most convenient large scale synthesis of α-(difluoromethyl)styrene DFMST
began with acetophenone 4 (Scheme 3, Table 2). Base-induced difluoromethylation
coupling was performed reacting this ketone 4 with difluoromethylphenyl sulfone 3
(
PhSO CF H) in the presence of excess of lithium bis(trimethylsilyl)amide (LiHMDS)
2 2
and led uneventfully to the formation of desired 1,1-difluoro-2-phenyl-1-(phenyl-
sulfonyl)propan-2-ol 5. However, a duration of base addition had a crucial impact on
the efficiency of this step. The resultant product was isolated with excellent, 94%
yield (lit. 74%) [16]. Alcohol 5 was converted using reductive desulfonylation into 1,1-
difluoro-2-phenylopropan-2-ol 6 in 86% yield (lit. 93%) [22]. The mechanism of the
reduction proposed by Prakash and Olah involved a transfer of an electron from a
magnesium atom to sulfur atom of phenylsulfonic group [22]. Metallic magnesium
used as a reducing agent, was activated by AcOH-NaOAc buffer. Concentration of
the buffer and composition of solvents used in the reaction influenced considerably
the process yield. Dehydration of resulting carbinol 6 using phosphorus pentoxide
afforded the desired α-(difluoromethyl)styrene 7 in 69% yield (lit. 61%) [15].
Scheme 3. Synthesis of α-(difluoromethyl)styrene 7 by nucleophilic difluoro-
methylation of acetophenone 4 with difluoromethylphenyl sulfone 3. Reagents and
conditions: First step: acetophenone 4 (2 equiv), PhSO CF H 3 (1 equiv), LiHMDS (2
2
2
equiv), THF-HMPA (10:1), -78°C, 6 h; Second step: Mg (20 equiv), AcOH-NaOAc
buffer (8mol/L), DMF-H O (5:1), RT, 4 h; Third step: P O (5 equiv), toluene, reflux, 5
2
2
5
h.
Page 8 of 17

Table 2. Three-step sequence to α-difluoromethylstyrene 7
,1-difluoro-2-
Difluoromethyl- phenyl-1-
1
1,1-Difluoro-2-
α-Difluoromethyl
g
Entry
Yield
phenyl sulfone (phenylsulfonyl) phenylpropan-2-ol styrene
propan-2-ol
b
d
1
2
3
4
3 (0.39 mmol) 5 (traces)
6 -
6 (17%)
7 -
-
a,c
a,c
a,c
a,c
a,d
a
3 (2.31 mmol) 5 (94%)
3 (2.35 mmol) 5 (67%)
3 (4.08 mmol) 5 (56%)
7 (15%)
7 -
6%
-
e
6 (traces)
a,f
a
6 (51%)
7 (58%)
17%
56%
a,f
a
5
3 (22.1 mmol) 5 (94%)
6 (86%)
7 (69%)
a
b
c
d
Isolated yield; 0.5 h addition of LiHMDS; 1.5 h addition of LiHMDS; 4 mol/L AcOH-NaOAc
e
f
buffer in H O; 8 mol/L AcOH-NaOAc buffer in suspension H O; 8 mol/L AcOH-NaOAc buffer in
2
2
g
DMF-H O (5:1); Isolated overall yield over three steps.
2
This three-step synthetic route towards difluoromethylstyrene using a nucleophilic
difluoromethylation followed by reductive desulfonylation and subsequent
dehydration was found to be selective, cost-effective, easy to implement and easily
scalable (up to 22 mmol) giving the desired gem-difluorinated styrenic monomer in
5
6% overall yield.
3
. Conclusion
In conclusion, we have developed an efficient and effective, three-step synthetic
route to non-commercially available functional aromatic gem-difluorinated monomer.
α-(Difluoromethyl)styrene (DFMST) was made available in gram scale using as a key
step the nucleophilic difluoromethylation with PhSO CF H 3. Difluoromethylating
2
2
agent, sulfone 3, was obtained with 69% overall yield, in two-step, easily scalable
Page 9 of 17

process that was 1.6 times more effective in comparison with those already reported
lit. 44%). Additionally, arranging last two steps of monomer synthesis literature
(
protocol in a reverse order i.e. first reductive desulfonylation and subsequent
dehydration improved significantly the efficiency of the sequence and afforded the
desired difluorinated styrenic monomer DFMST with 56% overall yield, allowing for
subsequent polymerization studies. Introduction of the fluorinated α-methylstyrene
derivative into a polymeric structures can greatly improve the physicochemical
properties and increase the thermal stability of the resultant materials. This is
currently a subject of ongoing studies.
4
. Experimental
4
.1. Materials and methods
1
NMR spectra were recorded in deuterated solvents at 300 MHz ( H), 75/101 MHz
1
3
19
1
(
(
C) and at 282 MHz ( F), calibrated using an internal reference: TMS ( H), CDCl
3
13
19
C) or CFCl ( F). Chemical shifts (δ) are quoted in parts per million (ppm) and
3
coupling constants (J) are measured in Hertz (Hz). The following abbreviations are
used to describe multiplicities s=singlet, d=doublet, t=triplet, m=multiplet, dd=doublet
of doublets, dt=doublet of triplets, ddt=doublet of doublets of triplets. Thin-layer
chromatography (TLC) was performed on coated silica gel plate Merck 60 F254
.
Visualisation of the reaction components was achieved using U.V. fluorescence (254
nm) and ceric ammonium molibdate (CAM) or KMnO solution stain. For purification
4
of products column chromatography was carried out over Merck silica gel 60 (0.063-
0
.2 mm). The reagents: Thiophenol (97%, Sigma-Aldrich), Chlorodifluoromethane
(99%, SynQuest Laboratories), 3-Chloroperoxybenzoic acid (m-CPBA, ≤77%, Sigma-
®
Aldrich),
Acetophenone
(ReagentPlus ,
99%,
Sigma-Aldrich),
Lithium
Page 10 of 17

bis(trimethylsilyl)amide solution (LiHMDS, 1M in THF, Sigma-Aldrich), Sodium
®
acetate (NaOAc, ≥99%, Sigma-Aldrich), Acetic acid (AcOH, ReagentPlus , ≥99%,
Sigma-Aldrich), Magnesium (grit, ≥99%, Sigma-Aldrich) and N,N-dimethyformamide
(DMF, 99.8%, Sigma-Aldrich) purchased from suppliers were used without further
purification. Dichloromethane (CH Cl ) and toluene were dried and distilled over
2
2
CaH . Diethylether (Et O) was dried and distilled over NaH. Tetrahydrofuran (THF)
2
2
was dried and distilled over Na. Methanol (MeOH) was dried and distilled over Mg
turnings. Solvents for chromatography were distilled prior to use.
4
4
.2 Procedures
.2.1. Difluoromethylophenyl sulfide 2
To a solution of MeONa in MeOH, prepared by reaction of sodium metal Na (4.88 g,
12 mmol) and dry methanol (35 mL), was added dropwise thiophenol 1 (4.41 g, 4.11
2
mL, 40 mmol). The resulting mixture was stirred at room temperature for 2 h, and
then placed in cooling bath, -78°C. To the cooled reaction mixture CF ClH (6.92 g, 80
2
mmol) was added. After 3 h the reaction was quenched with water (200 mL) and
extracted with CH Cl (3 × 200 mL). The combined organic layers were dried
2
2
(
Na SO ) and concentrated under reduced pressure. The residue was purified by
2 4
silica gel column chromatography using pentane as eluent. R = 0.40 (pentane).
f
Yield: 5.00 g, 31.2 mmol, 78%.
1
H NMR (300 MHz, CDCl ): δ 7.62-7.54 (m, 2H, H ), 7.44–7.33 (m, 3H, H ), 6.81 (t,
3
Ar
Ar
13
J = 57.0 Hz, 1H, CF H); C NMR (75 MHz, CDCl ): δ 135.5 (s, C ), 129.8 (d, J =
2
3
Ar
1
2.7 Hz, C ), 129.8-129.3 (m, C ), 126.3 (t, J = 3.0 Hz, C ), 121.2 (t, J = 275.1 Hz,
Ar Ar Ar
19
CF H); F NMR (282 MHz, CDCl ): δ -91.9 (d, J = 57.0 Hz, 2F, CF ). The NMR data
2
3
2
were in a good agreement with those already reported.
Page 11 of 17

4
.2.2. Difluoromethylophenyl sulfone 3
To a solution of difluoromethylphenyl sulfide 2 (3.98 g, 25 mmol) in dry CH Cl (69
2
2
mL) at 0 °C, a solid m-CPBA (15.9 g, 92.0 mmol) was added portionwise. The
reaction was then warmed to room temperature and left for overnight stirring. CH Cl2
2
(
50 mL) was then added and the mixture was washed with 10% aqueous Na SO (2
2 3
×
100 mL), 5% aqueous NaHCO (4 × 50 mL) and brine (2 × 100 mL), respectively.
3
Organic layer was dried (Na SO ) and concentrated under reduced pressure. The
2
4
residue was purified by silica gel column chromatography using CH Cl and hexane
2
2
as eluents (3:1). R = 0.40 (CH Cl /hexane, 3:1).
f
2
2
Yield: 4.24 g, 22.1 mmol, 88%
1
H NMR (300 MHz, CDCl ): δ 8.01 (dt, J = 8.7; 1.7 Hz, 2H, H ), 7.85-7.78 (m, 1H,
3
Ar
13
H ), 7.72–7.62 (m, 2H, H ), 6.20 (t, J = 53.4 Hz, 1H, CF H); C NMR (101 MHz,
Ar
Ar
2
CDCl ): δ 136,0 (s, C ), 131.9 (s, C ), 130.8 (s, C ), 129.7 (s, C ), 114.8 (t, J =
3
Ar
Ar
Ar
Ar
19
2
85.9 Hz, CF H); F NMR (282 MHz, CDCl ): δ -122.1 (d, J = 53.4 Hz, 2F, CF H).
2 3 2
The NMR data were in a good agreement with those already reported.
4
.2.3. 1,1-difluoro-2-phenyl-1-(phenylsulfonyl)propan-2-ol 5
To a solution of PhSO CF H 3 (4.24 g, 22.1 mmol) and acetophenone 4 (5.31 g, 5.15
2
2
mL, 44.1 mmol) in THF/HMPA (v/v, 10:1) cooled to -78 °C (cooling mixture of
isopropanol/dry ice) was added dropwise LiHMDS (1M in THF, 44.1 mL, 44.1 mmol).
Reaction was stirred for 6 h at -78 °C. Saturated aqueous NaCl (440 mL) was then
added at -78 °C, the residue was brought to room temperature and extracted with
Et O (3  440 mL). The combined organic layers were dried (Na SO ) and under
2
2
4
reduced pressure. The crude product was purified by silica gel column
Page 12 of 17

chromatography using hexane and CH Cl2 as eluents (1:3). Rf = 0.43
2
(
CH Cl /hexane, 3:1)
2 2
Yield: 6.52 g, 20.8 mmol, 94%.
1
H NMR (300 MHz, CDCl ): δ 7.87 (d, J = 7.8 Hz, 2H, H ), 7.74-7.66 (m, 1H, H ),
3
Ar
Ar
7
3
1
2
.61-7.48 (m, 4H, H ), 7.41-7.29 (m, 3H, H ), 3.85 (s, 1H, OH), 1.96 (t, J = 1.3 Hz,
Ar Ar
13
H, CH ); C NMR (101 MHz, CDCl ): δ 13.3 (s, C ), 135.8 (s, C ), 134.2 (s, C ),
3
3
Ar
Ar
Ar
30.8 (s, C ), 129.6 (s, C ), 129.0 (s, C ), 128.6 (s, C ), 127.0 (s, C ), 121.4 (t, J =
Ar
Ar
Ar
Ar
Ar
19
98.4 Hz, CF ), 77.3 (t, J = 21.2 Hz, (OH)CCF ), 25.36 (s, CH ); F NMR (282 MHz,
2
2
3
CDCl ): δ -105,9 (s, 2F, CF ). The NMR data were in a good agreement with those
3
2
already reported.
4
.2.4. 1,1-Difluoro-2-phenylopropan-2-ol 6
To a mixture of HOAc/NaOAc (1:1) buffer solution (119 mL, 8 mol/L) and DMF (322
mL) at room temperature was added sulfone 5 (6.51 g, 20.9 mmol). Magnesium
turnings (12.7 g, 521 mmol) were added portionwise over 1 h. The reaction mixture
was stirred at room temperature for 4 h followed by addition of water (625 mL). The
solution mixture was extracted with Et O (3  450 mL), and the combined organic
2
phase was washed with saturated NaHCO solution and brine, and then dried
3
(
Na SO ). After the removal of Et O, the crude product was purified by silica gel
2 4 2
column chromatography using hexane and AcOEt as eluents (5:1). R = 0.43
f
(hexane/AcOEt, 5:1)
Yield: 3.10 g, 18.0 mmol, 86%.
1
H NMR (300 MHz, CDCl ): δ 7.57-7.45 (m, 2H, H ), 7.44-7.27 (m, 3H, H ), 5.71
3
Ar
Ar
13
(
dd, J = 56.7, 56.2 Hz, 1H, CF H), 2.37 (s, 1H, OH), 1.65 (t, J = 1.6 Hz, 3H, CH ); C
2
3
NMR (75 MHz, CDCl ): δ 140.5 (s, C ), 128.5 (s, C ), 128.2 (s, C ), 125.9 (s, C ),
3
Ar
Ar
Ar
Ar
Page 13 of 17

19
1
17.0 (t, J = 249.1 Hz, CF H), 74.3 (t, J = 22.0 Hz, (OH)CCF ), 22.3 (s, CH );
F
2
2
3
NMR (282 MHz, CDCl ): δ -129.8 (dd, J = 276.1, 56.2 Hz, 1F, CF H), -131.1 (dd, J =
3
2
2
76.1, 56.8 Hz, 1F, CF H). The NMR data were in a good agreement with those
2
already reported.
4
.2.5 α-Difluoromethylstyrene 7
To a solution of 1,1-difluoro-2-phenylpropan-2-ol 6 (3.10 g, 18.0 mmol) in toluene (36
mL) was added P O (1.28 g, 9.02 mmol) and the mixture was stirred for 5 h at reflux.
2
5
The reaction was then allowed to cool to room temperature and poured into a
separating funnel charged with water (250 mL). After extracting with Et O (3  360
2
mL), the combined organic layers were dried (Na SO ) and concentrated under
2
4
reduced pressure. The residue was purified by silica gel column chromatography
using pentane as eluent. R = 0.47 (pentane). Yield: 1.91 g, 12.4 mmol, 69%.
f
1
H NMR (400 MHz, CDCl ): δ 7.51 (d, J = 6.3 Hz, 2H, H ), 7.46-7.35 (m, 3H, H ),
3
Ar
Ar
13
6
.42 (t, J = 55.3 Hz, 1H, CF H), 5.75 (s, 1H, C=CH ), 5.69 (s, 1H, C=CH ); C NMR
2 2 2
(
101 MHz, CDCl ): δ 141.9 (t, J = 19.9 Hz, H C=CCF H), 134.7 (s, C ), 128.6 (s,
3 2 2 Ar
C ), 128.5 (s, C ), 126.9 (s, C ), 118.9 (t, J = 9.5 Hz, H C=CCF H), 115.4 (t, J =
Ar
Ar
Ar
2
2
19
2
39.6 Hz, CF H); F NMR (282 MHz, CDCl ): δ = -113.6 (d, J = 55.3 Hz, 2F, CF H).
2 3 2
The NMR data were in a good agreement with those already reported.
Acknowledgements
Financial support by National Science Centre Poland is gratefully acknowledged
grant N N204 277240 to J.W.K.).
(
Page 14 of 17

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Supplementary Information (for Review Purposes)
Click here to download Supplementary Information (for Review Purposes): SI_DFMST_IMPROVED APPROACH TO LARGE-SCAL
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