Reaction of substituted phenols and alcohols with (E)-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd)

Article abstract of DOI:10.1016/j.jfluchem.2020.109456

Simple and convenient one-pot procedures for the preparation of ArOCH=CHCF₃, ROCH=CHCF₃ and CF₃CH=CHOArOCH = CHCF₃ starting from the industrial product HFCO-1233zd (CF₃CH=CHCl) are presented. These syntheses involve the reaction of 1233zd with phenols and alcohols in the presence of potassium hydroxide in DMF or pyridine solvent at elevated temperatures.

Full text of DOI:10.1016/j.jfluchem.2020.109456

JournalofFluorineChemistry232(2020)109456
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Reaction of substituted phenols and alcohols with (E)-1-chloro-3,3,3-
trifluoropropene (HFCO-1233zd)
Oleksii І. Mushta, Mikhail M. Kremlev, Andrey A. Filatov, Yurii L. Yagupolskii*
Institute of Organic Chemistry, NAS Ukraine, Murmanska st. 5, UA-02094 Kyiv, Ukraine
A R T I C L E I N F O
A B S T R A C T
Keywords:
Simple and convenient one-pot procedures for the preparation of ArOCH=CHCF3, ROCH=CHCF3 and
CF3CH=CHOArOCH = CHCF3 starting from the industrial product HFCO-1233zd (CF3CH=CHCl) are pre-
sented. These syntheses involve the reaction of 1233zd with phenols and alcohols in the presence of potassium
hydroxide in DMF or pyridine solvent at elevated temperatures.
(E)-1-chloro-3,3,3-trifluoropropene
O-nucleophile
Phenol derivatives
1. Introduction
(E)-1-Chloro-3,3,3-trifluoropropene (HFCO-1233zd) 1 belongs to
the modern class of hydrofluorochloroolefins that has a low global
warming potential (GWP) and no significant ozone depleting properties
[1a, b], It is used as a blowing agent and a solvent. Literature describing
the reaction chemistry of (E)-1-chloro-3,3,3-trifluoropropene is of lim-
ited scope and number of references. The existing patent literature is
mostly focused on 1233zd use in applications. Some citations disclose
reactions with hydroxy containing compounds [2–8], but there is no
systematic description of the reaction of (E)-1-chloro-3,3,3-tri-
fluoropropene 1 with O- and S- nucleophiles. An exception is the de-
tailed procedure for the preparation of 3,3,3-trifluoropropanal dimethyl
acetal from (E)-1-chloro-3,3,3-trifluoropropene and methanol in the
presence of KOH at 70 (or 100) oC [9]. We decided to perform a sys-
tematic study on the reactions of 1 with phenols and aliphatic alcohols
as representatives of O-nucleophiles.
Due to the steric influence of bulky CF3 group (in contrast to
chlorine atom) as well as to the electron withdrawing character of this
group one can assume nucleophile attack to =CCl moiety.
An important consideration is the H2O concentration in the reaction
mixture, thus three methods of O-anion generation were employed that
involve varying amount of water, as follows:
2.1. Method A. The treatment of substituted phenols with solid KOH in
anhydrous N,N-dimethylformamide
2. Results and discussion
2.2. Method B. The treatment of substituted phenols with aqueous KOH
solution (25 %) in N,N-dimethylformamide
It is noteworthy to outline that the main mechanism of nucleophilic
vinylic substitution via addition-elimination was investigated in details
by Prof. Zvi Rappoport [10a,b] and suggests the stereoconversion or
even retention of starting product configuration, especially upon action
of the oxygen nucleophiles.
The reaction of (E)-1-chloro-3,3,3-trifluoropropene 1 with sub-
stituted phenols and alcohols is described by the following general
scheme leading to form Z/E isomer mixtures:
⁎ Corresponding author.
E-mail address: Yagupolskii@ioch.kiev.ua (Y.L. Yagupolskii).
https://doi.org/10.1016/j.jfluchem.2020.109456
Received 30 September 2019; Received in revised form 16 December 2019; Accepted 18 December 2019
Availableonline23January2020
0022-1139/©2020ElsevierB.V.Allrightsreserved.

O.І. Mushta, et al.
JournalofFluorineChemistry232(2020)109456
Scheme 1. The treatment of olefin 1 with substituted penols. i) 1 eq. KOH, DMF, 80 °C 8 h.
2.3. Method C. The treatment of substituted phenols and alcohol with NaH
in anhydrous N,N-dimethylformamide
and water (3 eq. water to 1 eq. KOH) with 0.5 eq. of the diethylene
glycol, 1 mol% of Bu4NCl and (E)-1-chloro-3,3,3-trifluoropropene after
stirring 10 h at 80 °C gave product 8 in 20 % yield. When pyridine was
used instead of DMF, the yield of product 8 increased to 40 %. In no
case double addition was observed (Scheme 6).
2.6. Examples of method C
2.4. Examples of method A
This method utilized the pregeneration of the O-anion in DMF by
NaH treatment of the alcohols.
Recently we showed that chloroperfluoro-containing olefin, such as
1,2-dichloro-1,2-difluoro ethene, was capable of reacting with phenols
in the presence of potassium hydroxide. The reaction products con-
stitute olefins with an aryloxy group replacing the chlorine atom.
Reaction conditions were rather mild utilizing an open system at 80 °C
in DMF [11].
We investigated the reaction of (E)-1-chloro-3,3,3-trifluoropropene
with benzyl alcohol under anhydrous conditions using NaH. The result
was similar to that obtained by Method B, conversion of benzyl alcohol
was 50 % (Scheme 7).
The reaction of olefin 1 with hydroquinone in anhydrous conditions
under Argon using 2 eq. of sodium hydride at 80 °C after 10 h stirring
gave the mixture of products 5 and 9 as the E-isomers only (Scheme 8).
The treatment of (E)-1-chloro-3,3,3-trifluoropropene (1) with 1 eq.
of 2-methoxy-ethanol in DMF using 1 eq. of sodium hydride led to
product 7 formation in 20 % yield with predominant formation of E-
isomer (Scheme 9).
It was found that the treatment of (E)-1-chloro-3,3,3-tri-
fluoropropene (1) with substituted phenols 2 in the presence of 1 eq.
potassium hydroxide at 80 °C for 8 h gave corresponding products 3 as a
mixture of Z/E -isomers in various ratios depending on the phenol as
expected on the basis of literature precedent [10a,b] (Scheme 1). A
study devoted to the explanation of E/Z ratio of products formed is
needed but falls outside the scope of the present study due to the spe-
cific character of experiments that establish reaction mechanism
(thermodynamic or kinetic factors).
The reaction of olefin 1 with 2-(2-hydroxyethoxy)ethyl benzoate 10
was carried out using Method C. The sodium hydride was added to 2-
(2-hydroxyethoxy)ethyl benzoate followed by addition of (E)-1-chloro-
3,3,3-trifluoropropene. The reaction mixture was stirred 1 h at room
temperature and 10 h at 80 °C. The product 11 was isolated in 10 %
overall yield. E-isomer was the main product (Z/E = 1/13) (Scheme
10).
The (E)-1-chloro-3,3,3-trifluoropropene (1) also reacted with
2,2,3,3-tetrafluoropropan-1-ol in the presence of 1 eq. potassium hy-
droxide at 80 °C for 8 h to give (Z/E)-3,3,3-trifluoro-1-(2,2,3,3-tetra-
fluoropropoxy)propene 4 in 76 % yield (Z/E-ratio = 1/24) (Scheme 2).
The treatment of (E)-1-chloro-3,3,3-trifluoropropene (1) with di-
potassium hydroquinolate (obtained from 1 eq. of hydroquinone and 2
eq. of potassium hydroxide) in DMF at 80 °C for 8 h gave 1,4-di(3,3,3-
trifluoropropenyloxy)benzene 5 in only 10 % yield (molar ratio Z/E-
isomers 1/5) (Scheme 3).
2.7. Reaction of (E)-1-chloro-3,3,3-trifluoropropene with 2-
dimethylaminoethanole
In the reaction of 1 eq. of olefin 1 with 2 eq. of 2-dimethylami-
noethanol in open system with the addition of small amount DMF as a
solvent for olefin, at 80−85 °C for 11 h the product 12 was isolated in
72 % yield (Scheme 11).
2.5. Examples of method B
This method was used for the reaction of (E)-1-chloro-3,3,3-tri-
fluoropropene (1) with benzyl alcohol and aliphatic alcohols. In the
reaction of (E)-1-chloro-3,3,3-trifluoropropene with benzyl alcohol in
the presence of 1 eq. potassium hydroxide and 3 eq. of water at 80 °C
for 8 h the product 6 was obtained in 50 % yield (Z/E ratio = 1/9)
(Scheme 4).
3. Conclusion
Systematic study on the reactivity of (E)-1-chloro-3,3,3-tri-
fluoropropene (HFCO-1233zd) in the presence of base with O-nucleo-
philes such as substituted phenols and primary alcohols was described.
This work proved 1233zd’s ability to serve as promising starting ma-
terial to construct olefins of general structure CF3CH = CHOAr and
CF3CH = CHOR. The solvent of choice is DMF but in some instances
pyridine is the preferred, reaction temperature around 80 °C was ne-
cessary to achieve reasonable yields. The alcohols investigated include
polyols that are common ingredients in blowing agent formulations.
The treatment of (E)-1-chloro-3,3,3-trifluoropropene (1) with 1 eq.
of 2-methoxy-ethanol in a solution of potassium hydroxide in DMF and
water (3 eq. water to 1 eq. KOH) in the presence 1 mol% Bu4NCl gave
product 7, but olefin conversion after 10 h at 80 °C, according to 19F
NMR, was only 10 %. The product 7 was not isolated. (Scheme 5)
The interaction of aqueous potassium hydroxide solution in DMF
Scheme 2. The reaction of olefin 1 with telomere alcohol. i) 1 eq.
KOH, DMF, 80 °C 8 h.
2

O.І. Mushta, et al.
JournalofFluorineChemistry232(2020)109456
Scheme 3. The treatment of olefin 1 with hydroquinone; i) 2 eq.
KOH, DMF, 80 °C 8 h.
4. Experimental
(arom. C), 149.17 (q, 3JCF = 5.5 Hz, OCH=), 130.01 (arom. C), 129.91
1
(arom. C), 124.63 (arom. C), 122.87 (q, JCF = 267 Hz, CF3), 117.24
NMR spectra of compounds isolated were recorded on a Varian
UNITY-Plus 400 (1H, 399.98 MHz, 19F, 376.49 MHz) and 13C NMR-
spectra were recorded on a Bruker AVANCE DRX 500 instrument at
125,71 MHz in CDCl3. The chemical shifts are given in units of δ (ppm).
External standards were used in all cases (1H, 13C: Me4Si, 19F: CCl3F).
Elemental analyses were carried out in the Analytical Laboratory of the
Institute of Organic Chemistry, NAS of Ukraine, Kyiv. Purification of
products by column chromatography was performed on Silica gel
70–230 mesh (Aldrich) with hexane: dichloromethane eluent (3:1 by
volume).
(arom. C), 99.21 (q, 2JCF = 35.6 Hz, CF3CH=); 19F NMR (376.49 MHz,
3
CDCl3): δ -58.4 (d, 3 F, JHF = 7 Hz).
Analysis: Found: %C 57.48; %H 3.53. C9H7F3O. Calcd.: %C 57.45; %
H 3.75.
4.3. 1-(4-Methoxyphenyl)-3,3,3-trifluoropropene 3b
Colorless liquid. Yield 73 %, b.p. 50−56 °C (0.4 mm Hg).
4.3.1. E-isomer
Isomer structures were determined by NMR 1H and 19F data. Both
isomers are characterized by chemical shift in NMR19F as (-56÷-57
ррm) for Z-isomer and
1H NMR (400 MHz, CDCl3): δ 3.79 (s, CH3), 5.24 (m, 1H, CH=),
3
3
6.89 (d, 2H, JHH = 7.5 Hz, arom. H), 7.07 (d, 2H, JHH = 7.5 Hz,
arom. H), 7.25 (dd, 1H, 3JHH = 12 Hz, 4JHF = 1.4 Hz, CH=); 13C NMR
3
(-59÷-61 ррm) for E-isomer; the most specific J-constants are
presented in 1H NMR spectra: 3JHH≈8 Hz for Z-изомера и 3JHH≈12 Hz
for E-isomer.
(125.71 MHz, CDCl3): δ 156.89 (arom. C), 153.17(q, JCF = 8.1 Hz,
OCH=), 150.77 (arom. C), 124.8 (q, 1JCF = 267 Hz, CF3), 119.5 (arom.
2
C), 118.5 (arom. C), 114.96 (arom. C), 114.83 (arom. C), 99.8 (q, JCF
= 34.5 Hz, CF3CH=); 19F NMR (376.49 MHz, CDCl3): δ -60.25 (br.s, 3
4.1. The treatment of substituted phenols with KOH in anhydrous N,N-
dimethylformamide – Method A
F).
4.3.2. Z-isomer
1H NMR (400 MHz, CDCl3): δ 3.8 (s, CH3), 4.9 (m, 1H, CH=), 6.66
4.1.1. General procedure
(m, 1H, CH=) 6.88 (d, 2H, 3JHH = 8 Hz, arom. H), 7.04 (d, 2H, 3JHH
=
A mixture of corresponding substituted phenol or telomere alcohol
(40 mmol), of potassium hydroxide (40 mmol) and anhydrous DMF (30
ml) was stirred at room temperature till the entire potassium hydroxide
was reacted with phenol. Then of of (E)-1-chloro-3,3,3-trifluoropropene
(40 mmol) was added to solution and reaction mixture was stirred for 8
h at 80−90 °C. Reaction mixture was cooled to room temperature and
poured into water. The organic layer was extracted with MTBE (methyl-
tert-butyl ether), the extract was washed with 5 % aqueous potassium
hydroxide, followed by water and dried over sodium sulfate. The sol-
vent was evaporated under reduced pressure. The crude product was
purified by distillation or column chromatography.
8 Hz, arom. H); 13C NMR (125.71 MHz, CDCl3): δ 156.62 (arom. C),
3
1
150.31(q, JCF = 5.9 Hz, OCH=), 149.31 (arom. C), 124.8 (q, JCF
=
267 Hz, CF3), 119.5 (arom. C), 118.5 (arom. C), 114.96 (arom. C),
114.83 (arom. C), 99.20 (q, JCF = 35.2 Hz, CF3CH=); 19F NMR
2
(376.49 MHz, CDCl3): δ -57.9 (br s, 3 F).
Analysis: Found: %C 54.8; %H 3.86. C10H9F3O2. Calcd.: %C 55.05;
% H 4.16.
4.4. 4-(3,3,3-trifluoropropenyloxy)benzaldehyde 3c
Yellow liquid. Yield 40 %, b.p. 74−78 °C (15 mm Hg).
4.4.1. E-isomer
4.2. 1-Phenoxy-3,3,3-trifluoropropene 3a
3
1H NMR (400 MHz, CDCl3): δ 5.59 (m, 1 H), 7.17(d, 2H, JHH = 8
Colorless liquid. Yield 70 %, b.p. 69−76 °C (16 mm Hg).
3
4
Hz, arom. H) 7.34 (dd, 1H, JHH = 12 Hz, JHF = 1.6), 7.93 (d, 2H,
3JHH = 8 Hz, arom. H), 9.97 (s, 1 H); 13C NMR (125.71 MHz, CDCl3): δ
4.2.1. E-isomer
1H NMR (400 MHz, CDCl3): δ 5.37 (m, 1H, CH=), 7.05 (d, 2H, 3JHH
3
190.56 (CO), 160.10 (arom. C), 149.69 (q, JCF =8.1 Hz, OCH=),
3
1
= 7.8 Hz, arom. H), 7.17 (m, 1H, arom. H), 7.25 (dd, 1H, JHH = 12
133.01 (arom. C), 132.03 (arom. C) 123.7 (q, JCF = 267 Hz, CF3),
4
Hz, JHF = 1.6 Hz, CH=), 7.37 (m, 2H, arom. H); 13C NMR (125.71
117.63 (arom. C), 102.65 (q, JCF = 34.5 Hz, CF3CH=); 19F NMR
2
3
3
4
MHz, CDCl3): δ 156.62 (arom. C), 151.92 (q, JCF = 8 Hz, OCH=),
(376.49 MHz, CDCl3): δ -61.3 (dd, 3 F, JHF = 7.6 Hz, JHF = 1.7 Hz).
130.01 (s, arom. C), 129.91 (arom. C,), 124.96 (arom. C), 124.8 (q, 1JCF
2
= 269 Hz, CF3), 117.99 (arom. C), 99.9 (q, JCF = 34 Hz, CF3CH=);
4.4.2. Z-isomer
19F NMR (376.49 MHz, CDCl3): δ -60.8 (dd, 3 F, 3JHF = 7.5 Hz, 4JHF
1.6 Hz).
=
1H NMR (400 MHz, CDCl3): δ 5.18 (m, 1 H), 6.84 (d, 1H, 3JHH = 6.8
3
3
Hz), 7.19 (d, 2H, JHH = 8 Hz, arom. H), 7.93 (d, 2H, JHH = 8 Hz,
arom. H), 9.97 (s, 1 H); 13C NMR (125.71 MHz, CDCl3): δ 190.56 (CO),
159.64 (arom. C), 147.21 (q, 3JCF = 5.9 Hz, OCH=), 132.55 (arom. C),
4.2.2. Z-isomer
1H NMR (400 MHz, CDCl3): δ 4.9 (m, 1H, CH=), 6.74 (d, 1H, CH=,
3JHH = 6.7 Hz), 7.04 (d, 2H, JHH = 8 Hz, arom. H), 7.17 (m, 1H, arom.
H), 7.37 (m, 2H, arom. H); 13C NMR (125.71 MHz, CDCl3): δ 156.72
131.99 (arom. C) 123.7 (q, JCF = 267 Hz, CF3), 117.63 (arom. C),
1
102.65 (q, 2JCF = 35.2 Hz, CF3CH=); 19F NMR (376.49 MHz, CDCl3): δ
3
-58.6 (d, 3 F, JHF = 7.5 Hz).
Scheme 4. The reaction of olefin 1 with benzyl alcohol; i) 1 eq.
KOH, 3 eq. H2O, DMF, 80 °C 8 h.
3

O.І. Mushta, et al.
JournalofFluorineChemistry232(2020)109456
Scheme 5. The reaction of olefin 1 with 2-methoxy-ethanol; i) 1
eq.KOH, 3 eq. H2O, DMF, 1 mol% Bu4NCl, 80 °C, 10 h.
Scheme 6. The reaction of olefin 1 in the aqueous potassium
hydroxide solution in mixture solvent DMF and water; i) 2 eq.
1, 2 eq. KOH, 3 eq.H2O, DMF, 1 mol% Bu4NCl, 80 °C, 10 h; ii)
2 eq. 1, 2 eq. KOH, 3 eq. H2O, Py, 1 mol% Bu4NCl, 80 °C, 10 h.
3
Analysis: Found: %C 55.28; %H 3.30. C10H7F3O2. Calcd.: %C 55.57;
(376.49 MHz, CDCl3): δ -55.1 (d, 3 F, JHF = 8 Hz), -124.2 (s, 2 F),
% H 3.26.
-136.2 (d, 2 F, JHF = 48.9 Hz).
Analysis: Found: %C 31.79 %H 2.34. C6H7F7O. Calcd.: %C 31.87; %
H 2.23.
4.5. 1-(4-nitrophenyl)-3,3,3-trifluoropropene 3d
Yellow oil (after flash chromatography (hexane/CH2Cl2: 75/25)).
Yield 30 %.
4.7. (E)-4,4’-Di(3,3,3-trifluoropropenyloxy)benzene 5
Colorless oil. Yield 10 %.
1H NMR (400 MHz, CDCl3): δ 5.37 (m, 2 H), 7.2 (br s, 4H, arom. H),
4.5.1. E-isomer
3
1H NMR (400 MHz, CDCl3): δ 5.6 (m, 1 H), 7.20(d, 2H, JHH = 8.1
3
7.24 (dm, 2H, JHH = 12.8 Hz); 13C NMR (125.71 MHz, CDCl3): δ
3
4
152.53 (arom. C.), 151.86 (q, 3JCF = 8.1 Hz, OCH=), 124.27 (q. 1JCF
=
Hz, arom. H) 7.34 (dd, 1H, JHH = 12.3 Hz, JHF = 1.8 Hz), 7.93 (d,
2H, 3JHH = 8.1 Hz, arom. H); 13C NMR (125.71 MHz, CDCl3): δ 164.10
2
267 Hz, CF3), 119.66 (arom. C), 100.39 (q JCF = 34.5 Hz, CF3CH=);
3
1
19F NMR (376.49 MHz, CDCl3): δ -61.0 (dd, 6 F, 3JHF = 6.1 Hz, 4JHF
1.6 Hz).
=
(arom. C), 149.21 (q, JCF = 8 Hz, OCH=), 144.32 (arom. C), 126.09
(arom. C) 123.58 (q, JCF-267 Hz, CF3), 117.46 (arom. C), 103.55 (q,
2JCF = 34.1 Hz, CF3CH=); 19F NMR (376.49 MHz, CDCl3): δ -60.5 (dd,
Analysis: Found: %C 48.35 %H 2.76. C12H8F6O2. Calcd.: %C 48.34;
3
4
3 F, JHF = 6.76 Hz, JHF = 1.7 Hz).
% H 2.7.
4.5.2. Z-isomer
1H NMR (400 MHz, CDCl3): δ 5.25 (m, 1 H), 6.8 (d, 1H, 3JHH = 6.7
Hz), 6.95 (d, 2H, 3JHH = 8.5 Hz, arom. H), 7.93 (d, 2H, 3JHH = 8.5 Hz,
arom. H); 13C NMR (125.71 MHz, CDCl3): δ 160.68 (arom. C), 146.74
(q, 3JCF = 5.5 Hz, OCH=), 141.27 (arom. C), 126.02 (arom. C) 125.58
4.8. The treatment of alcohols with KOH solution (25 %) in N,N-
dimethylformamide – method B
4.8.1. General procedure
1
2
A mixture of corresponding alcohol (40 mmol), potassium hydro-
xide (80 mmol), in water (120 mmol) [in case 2-methoxy ethanol and
diethylene glycol it was used 1 %-mol of Bu4NCl as phase transfer] and
DMF (30 mL) was mixed together and stirred at room temperature till
the entire potassium hydroxide was dissolved. Then of of (E)-1-chloro-
3,3,3-trifluoropropene (80 mmol) was added to solution and reaction
mixture was stirred for 8 h at 80−90 °C. The reaction mixture was
cooled to room temperature and poured into water. Organic layer was
extracted with MTBE, the organic layer was washed with 5 % aqueous
potassium hydroxide, followed by water and dried over sodium sulfate.
The solvent was evaporated under reduced pressure and the crude
product was purified by distillation or column chromatography.
(q, JCF = 267 Hz, CF3), 117.06 (arom. C), 102.47 (q, JCF = 35.1 Hz,
CF3CH=); 19F NMR (376.49 MHz, CDCl3): δ -57.8 (d, 3 F, JHF = 8.5
3
Hz).
Analysis: Found: %C 46.64 %H 2.49; N 6.17. C9H6F3NO3. Calcd.:
%C 46.37; % H 2.59;
N 6.01.
4.6. 1-(2,2,3,3-tetrafluoropropoxy)-3,3,3-trifluoro-propene 4
Colorless liquid. Yield 76 %, b.p. 120−122 °C
4.6.1. E-isomer
1H NMR (400 MHz, CDCl3): δ 4.17 (t, 2H, 3JHH = 11.8 Hz), 5.15(m,
1 H), 5.93 (dm, 1H, JHF = 52.9 Hz), 7.0 (d, 1H, 3JHH = 13.7 Hz); 13
C
2
4.9. ((E)-(3,3,3-Trifluoropropenyloxy)methyl)benzene 6
3
NMR (125.71 MHz, CDCl3): δ 153.25 (q, JCF = 7.7 Hz, OCH=),
1
1
2
124.06 (q, JCF = 267 Hz, CF3), 113.88 (tt, JCF = 250.5 Hz, JCF
=
=
Colorless liquid. Yield 50 %, b.p. 79−80 °C (14 mm Hg).
1H NMR (400 MHz, CDCl3): δ 4.84 (s, 2 H), 5.1 (m, 1 H), 7.13 (dd,
1H, 3JHH = 12.6 Hz; 4JHF = 1.6 Hz), 7.38 (m, 5 H, arom. H); 13C NMR
28.1 Hz), 108.94 (tt, 1JCF = 250 Hz, 2JCF = 35.6 Hz), 97.03 (q, 2JCF
34.1 Hz, CF3CH=) 66.63 (2JCF = 29.6 Hz, CH2); 19F NMR (376.49
MHz, CDCl3): δ -57.2 (d, 3 F, 3JHF = 4 Hz), -121.52 (s, 2 F), -135.4 (d, 2
F, JHF = 52.9 Hz).
3
(125.71 MHz, CDCl3): δ 154.28 (q, JCF = 8.0 Hz, OCH=), 143.57
(arom. C), 128.76 (arom. C), 128.61 (arom. C), 127.7 (arom. C), 124.83
(q, 1JCF = 267 Hz, CF3), 95.02 (q, 2JCF = 34.6 Hz, CF3CH=); 19F NMR
3
4.6.2. Z-isomer
(376.49 MHz, CDCl3): δ -59.82 (d, 3 F, JHF = 6.3 Hz).
1H (400 MHz, CDCl3): δ 3.9 (t, 2H, 3JHH = 11.4 Hz), 4.86 (m, 1 H),
Analysis: Found: %C 59.14; %H 4.46. C10H9F3O. Calcd.: %C 59.41;
% H 4.41.
5.96 (dm, 1H, 2JHF = 48.9 Hz), 6.9 (d, 1H, JHH = 11.6 Hz); 19F NMR
3
Scheme 7. The anhydrous condition of the reaction of olefin 1
with sodium benzylate; i) 1 eq. NaH, DMF, 80 °C 10 h.
4

O.І. Mushta, et al.
JournalofFluorineChemistry232(2020)109456
Scheme 8. The reaction of olefin 1 with hydroquinone under
anhydrous condition; i) 2 eq. NaH, DMF, 80 °C 10 h.
Scheme 9. The interaction of olefin 1 with sodium 2-metoxy-
ethylate; i) 1 eq. NaH, DMF, 80 °C 10 h.
Scheme 10. The method utilizing the pregeneration of the O-
anion in DMF by NaH treatment of the alcohols.; i) 1 eq. NaH,
DMF, 80 °C 10 h.
Scheme 11. The reaction of olefin 1 with 2-dimethylaminoetha-
nole; i) 1 eq. of olefin 1 with 2 eq. of 2-dimethylaminoethanol,
DMF, 80 °C 11 h.
4.10. 2-(2-(3,3,3-Trifluoroprop-1-enyloxy)ethoxy)ethanol 8
4.12. (E)-4,4’-di(3,3,3-trifluoropropenyloxy)benzene 5
Colorless oil. Yield 20 % (reaction in the DMF); 40 % (reaction in
pyridine);
Colorless oil. Yield 16 %.
4.13. ((E)-(3,3,3-Trifluoropropenyloxy)methyl)benzene 6
4.10.1. E-isomer
Colorless liquid. Yield 50 %, b.p. 79−80 °C (14 mm Hg).
1H NMR (400 MHz, CDCl3): δ 2.1 (br s, 1 H), 3.6 (t, 2H, 3JHH = 4.3
3
Hz), 3.74 (m, 4 H), 3.93 (m, 2 H), 4.98 (m, 1 H), 7.5 (dd, 1H, JHH
=
12.7, 4JHF = 1.6 Hz); 13C NMR (125.71 MHz, CDCl3): δ 154.58 (q, 3JCF
4.14. 1-(2-methoxy-ethoxy)-3,3,3-Trifluoro-propene 7
1
2
= 8.0 Hz, OCH=), 124.74 (q. JCF = 266.3 Hz, CF3), 94.5 (q JCF
=
33.7 Hz, CF3CH=), 72.61, 69.7, 69.09, 61.61; 19F NMR (376.49 MHz,
Yellow oil. Yield 20 %.
3
CDCl3): δ -59.9 (d, 3 F, JHF = 6.5 Hz).
4.14.1. E-isomer
3
1H NMR (400 MHz, CDCl3): δ 3.4 (s, CH3), 3.61 (t, 2H, JHH = 4.6
3
3
4.10.2. Z-isomer
Hz), 3.92 (t, 2H, JHH = 4.6), 4.98 (m, 1 H), 7.07 (dm, 1H, JHH
=
1H NMR (400 MHz, CDCl3): δ 2.1 (brs, 1 H), 3.6 (t, 2H, 3JHH = 4.3
Hz), 3.74 (m, 4 H), 3.93 (m, 2 H), 4.63 (m, 1 H), 7.5 (m 1 H); 19F
4
3
12.7, JHF = 1.6 Hz); 13C NMR (125.71 MHz, CDCl3): δ 154.6 (q, JCF
= 8.1 Hz, OCH=), 124.78 (q, 1JCF = 266.3 Hz, CF3), 94.42 (q, 2JCF
=
3
33.7 Hz, CF3CH=), 70.42, 69.64, 59.08; 19F NMR (376.49 MHz,
(376.49 MHz, CDCl3): δ -57.8 (d, 3 F, JFH = 6.5 Hz).
3
Analysis: Found: %C 42.25; %H 5.51. C7H11F3O3. Calcd.: %C 42.01;
% H 5.54
CDCl3): δ -59.86 (d 3 F, JFH = 5.8 Hz).
4.14.2. Z-isomer
1H NMR (400 MHz, CDCl3): δ 3.38 (s, CH3), 3.64 (t, 2H, 3JHH = 4.3
Hz), 4.08 (t, 2H, 3JHH = 4.3), 4.62 (m, 1 H), 6.4 (d, 1H, 3JHH = 6.9 Hz);
4.11. The treatment of substituted phenols and alcohols with NaH in
anhydrous N,N-dimethylformamide – method C
19F NMR (376.49 MHz, CDCl3): δ -59.9 (d, 3 F, JFH = 8.5 Hz).
3
Analysis: Found: %C 42.45; %H 5.26. C6H9F3O2. Calcd.: %C 42.36;
% H 5.33
4.11.1. General procedure
To suspension of sodium hydride (40 mmol) in anhydrous DMF (30
mL) at ambient temperature under argon and stirring was slowly added
corresponding alcohol (40 mmol). After observed termination of hy-
drogen evolution the reaction mixture was stirred for 10 min and of (E)-
1-chloro-3,3,3-trifluoropropene (40 mmol) was added dropwise. The
reaction mixture was then stirred for 10 h at 80 °C. After end of reaction
mixture was cooled to room temperature and poured into water. The
organic layer was extracted with MTBE, the extract was washed with 5
% aqueous potassium hydroxide, followed by water and dried over
sodium sulfate. The solvent was evaporated under reduced pressure.
The crude product was purified by flash column chromatography.
4.15. (E)-4-(3,3,3-Trifluoro-propenyloxy)phenol 9
Dark red oil. Yield 17 %.
1H NMR (400 MHz, CDCl3): δ 5.07 (s, 1H-OH); 5.22 (m, 1 H);
6.81(d, 2H, 3JHH = 8.4 Hz, arom. H); 6.91 (d, 2H, 3JHH = 8.4 Hz, arom.
H); 7.18 (d, 1H 3JHH 13.6 Hz); 19F NMR (376.49 MHz, CDCl3): δ -60.41
3
(d, 3 F, JHF = 7.8 Hz).
Analysis: Found: %C 52.96; %H 3.7. C9H7F3O3. Calcd.: %C 52.95; %
H 3.46
5

O.І. Mushta, et al.
JournalofFluorineChemistry232(2020)109456
266.7 Hz, CF3), 94.04 (q JCF = 34.4 Hz, CF3CH=), 67.90, 57.59,
45.48; 19F NMR (CDCl3, 376.49 MHz): δ -60.19 (d, 3 F, 3JHF = 7.8 Hz).
Analysis: Found: %C 45.88; %H 6.61; %N 7.64. C7H12F3NO. Calcd.:
%C 45.90; % H 6.60; N 7.65
2
4.16. 2-(2-Hydroxyethoxy)ethyl benzoate 10
To solution of diethylene glycol (30 mmol) and of triethyl amine (30
mmol) in anhydrous diethyl ether (20 mL) at 0 °C benzoyl chloride (30
mmol) was added slowly. Reaction mixture was stirred for 4 h then
poured into water. Organic layer was extracted with diethyl ether, the
extract was washed with 5 % aqueous potassium hydroxide, followed
by water and dried over sodium sulfate. The solvent was evaporated
under reduced pressure. The crude product was purified by flash
column chromatography.
Declaration of competing interest and authorship conformation
form
All authors have participated in (a) conception and design, or ana-
•
lysis and interpretation of the data; (b) drafting the article or re-
vising it critically for important intellectual content; and (c) ap-
proval of the final version.
Colorless oil. Yield 80 %.
NMR 1H (400 MHz, CDCl3): δ 8.04 (m, 2H, arom. H); 7.54 (m, 1H,
arom. H); 7.41 (m, 2H arom. H); 4.49 (t, 2H, CH2, 3JHH = 4.8 Hz); 3.89
This manuscript has not been submitted to, nor is under review at,
•
3
3
3
(t, OH, JHH = 4.8 Hz); 3.84 (t, 2H, CH2, JHH = 4.8 Hz); 3.75 (t, 2H,
another journal or other publishing venue.
3
CH2, JHH = 4.4 Hz); 3.65 (t, 2H, CH2, JHH = 4.4 Hz); 13C NMR
(125.71 MHz, CDCl3): δ 166.46 (COO), 132.96 (arom. C), 130.03
(arom. C), 129.63 (arom. C), 128.32 (arom. C), 69.16, 63.89.
Analysis: Found: %C 62.70; %H 6.72. C11H14O4. Calcd.: %C 62.85;
% H 6.71
The authors have no affiliation with any organization with a direct
•
or indirect financial interest in the subject matter discussed in the
manuscript
References
4.17. (E)-2-(2-(3,3,3-Trifluoroprop-1-enyloxy)ethoxy)ethyl benzoate 11
[1] (a) Cheryl Hogue, Chem. Eng. News Archive 89 (49) (2011) 31–32;
(b) Henri Groult, Frederic Leroux, Alain Tressaud in Modern Synthesis Processes
and Reactivity of Fluorinated Compounds Elsevier, (2016), pp. 52–56.
[2] R.P. Ruh, Production of fluorine-substituted ethylenyccaly unsaturated ethers, US
Patent 2,739,987, (1956);.
Yellow oil. Yield 10 %.
1H NMR (400 MHz, CDCl3): δ 8.02 (m, 2H, arom. H); 7.52 (m, 1H,
3
[3] Komata Takeo, Hosoi Kenji, Process for producing 3,3,3-trifluoropropionaldehyde,
Central Glass Co., Ltd; Pat., WO2007/37119A1, (2007);.
arom. H); 7.37 (m, 2H, arom. H); 7.04 (d, 1H, CH=, JHH = 11 Hz);
4.95 (m, 1H, CH=) 4.47 (t, 2H, CH2, 3JHH = 4.5 Hz); 3.85 (m, 6 H); 19
F
[4] Komata Takeo et al., Process for producing 3,3,3-trifluoropropionic acid, Pat.
EP1950191 A1, (2008);.
3
NMR (376.49 MHz, CDCl3): δ -59.8 (d, 3 F, JHH = 5.8).
[5] Yamazaki Tacachi, Miyazaki Eisuke, Takada Naoto, Methods for producing 3,3,3-
trifluoropropanol, Pat. JP5816037 (2015);.
Analysis: Found: %C 55.30; %H 5.07. C14H15F3O4. Calcd.: %C
55.27; % H 4.97
[6] A. Paul et al., Process for the preparation of tetrafluoropropene, Pat., WO2016/
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[7] Liu Ya Qun, Huang Hong Min, Methods for producing solvents derived from 1-
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quid crystal composition and liquid crystal display element. Pat., JP6299011,
(2018);.
4.18. N,N-Dimethyl-1-((E)-3,3,3-trifluoropropenyloxy)-ethylamine 12
A solution of 34 mmol of (E)-1-chloro-3,3,3-trifluoropropene with
68 mmol of 2-dimethylaminoethanole, and 50 ml of DMF in open
system, was stirred for 11 h at 80−85 °C. The reaction mixture was
cooled to room temperature and poured into water. The organic layer
was extracted with MTBE, the extract was washed with water and dried
over sodium sulfate. The solvent was evaporated under reduced pres-
sure. The crude product was isolated by fractional distillation.
Colorless liquid. Yield 72 %, b.p. 86−88 °C (20 mm Hg):
[9] T. Komata, S. Akiba, K. Hosoi, K. Ogura, Convenient synthesis of 3,3,3-tri-
fluoropropanoic acid by hydrolytic oxidation of 3,3,3-trifluoropropanal dimethyl
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[10] (a) Z. Rappoport, B. Avramovitch, Nucleophilic Attacks on Carbon-Carbon Double
Bonds. 28.Complete and Partial Stereoconversion in the Substitution of Methyl (E)-
and Z)-/3-Chloro-a-cyano-p-nitrocinnamates by Nucleophiles, J. Org. Chem. 47
(1982) 1397–1408;
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Substitution. Recent Developments, Acc.Chem.Res 25 (1992) 474–479.
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chloro-1,2-difluoroethenes, J. Fluorine Chem. 126 (2005) 1307–1311.
1H NMR (400 MHz, CDCl3): δ 7.05 (d, 1H, 3JHH 12.8 Hz,), 4.94 (m, 1
H), 3.83 (t, 2H, 3JHH = 5.4 Hz), 2.61 (t, 2H, 3JHH = 5.4 Hz), 2.27 (s, 6
3
1
H); 13C NMR:154.41 (q, JCF = 7.5 Hz, OCH=), 124.77 (q. JCF
=
6