Photo-on-Demand Base-Catalyzed Phosgenation Reactions with Chloroform: Synthesis of Arylcarbonate and Halocarbonate Esters

Article abstract of DOI:10.1021/acs.joc.1c01210

Carbonate esters are utilized as solvents and reagents for C1 building blocks in organic synthesis. This study reports a novel photo-on-demand in situ synthesis of carbonate esters with CHCl3 solutions containing a mixture of an aromatic or haloalkyl alcohol having relatively high acidity, and an organic base. We found that the acid-base interaction of the alcohol and base in the CHCl3 solution plays a key role in enabling the photochemical reaction. This reaction allows practical syntheses of diphenyl carbonate derivatives, haloalkyl carbonates, and polycarbonates, which are important chemicals and materials in industry.

Full text of DOI:10.1021/acs.joc.1c01210

pubs.acs.org/joc
Article
Photo-on-Demand Base-Catalyzed Phosgenation Reactions with
Chloroform: Synthesis of Arylcarbonate and Halocarbonate Esters
Yuka Hashimoto, Sasuga Hosokawa, Fengying Liang, Yuto Suzuki, Namin Dai, Gegen Tana, Kazuo Eda,
Toshifumi Kakiuchi, Takashi Okazoe, Hidefumi Harada, and Akihiko Tsuda*
Cite This: J. Org. Chem. 2021, 86, 9811−9819
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: Carbonate esters are utilized as solvents and reagents
for C1 building blocks in organic synthesis. This study reports a
novel photo-on-demand in situ synthesis of carbonate esters with
CHCl3 solutions containing a mixture of an aromatic or haloalkyl
alcohol having relatively high acidity, and an organic base. We
found that the acid−base interaction of the alcohol and base in the
CHCl3 solution plays a key role in enabling the photochemical
reaction. This reaction allows practical syntheses of diphenyl
carbonate derivatives, haloalkyl carbonates, and polycarbonates,
which are important chemicals and materials in industry.
academic and industrial settings. To overcome this problem
and the environmental concerns of phosgene, halocarbonate
esters are expected to be phosgene substitutes.2
INTRODUCTION
■
Halocarbonate esters have higher reactivity for nucleophilic
substitution reactions than their corresponding nonhalogen-
ated carbonate esters. The attached halogen enhances the
electrophilicity of the carbonyl carbon as well as the leaving
ability of the substituted alcohol group. With this property, one
can control the reactivity of the carbonate esters through
substitution of the halogen, and utilize them as a phosgene
substitute. Phosgene (COCl2) is a versatile C1 building block
in organic synthesis due to its high reactivity, utility, and cost
efficiency (Scheme 1, reaction 1).1 However, its high toxicity
hinders its convenient use in organic synthesis in both
Prior to the use of halocarbonate esters, it was known that
diphenyl carbonate (DPC) enables some phosgenation
reactions through a transesterification reaction. DPC has the
advantage of a relatively high leaving ability of the aromatic
phenoxy group (reaction 2).3 For example, some industrial
production methods for polycarbonates (PCs) are actually
carried out with DPC and diols such as bisphenol A (BPA).4
However, this process can only replace some phosgenation
reactions in terms of the reactivity, cost, and product quality.
For these reasons, the halocarbonate esters are expected to
extend the replacement of the phosgenation reactions.5 There
are, however, some essential problems: both the halocarbonate
esters and arylcarbonate esters are themselves synthesized with
COCl2, whose high reactivity allows reaction with acidic
alcohols having low nucleophilicity.2,6 Furthermore, industrial
production of DPC is attained through multistep syntheses
starting from CO2 and ethylene oxide (EO), which also
exhibits high toxicity and explosibility.4 This background
motivated us to develop a simple safe method of synthesizing
reactive carbonate esters.7 In the present study, we report a
novel in situ photo-on-demand synthesis of arylcarbonate and
halocarbonate esters with a chloroform (CHCl3) solution
Scheme 1. Syntheses of Carbonate Esters: (1 and 2)
Conventional Reactions, (3) Our Previously Reported
Reaction, and (4) the New Reaction Developed in This
Study
Received: May 24, 2021
Published: June 29, 2021
https://doi.org/10.1021/acs.joc.1c01210
© 2021 American Chemical Society
J. Org. Chem. 2021, 86, 9811−9819
9811

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
containing a mixture of the corresponding aryl or haloalkyl
alcohol and an organic base.
Table 1. Photochemical Syntheses of Carbonate Esters with
CHCl3 Solutions Containing an Alcohol and an Organic
Base
a
We previously reported the photochemical production of
COCl2 with CHCl3 and successfully applied it to practical
organic syntheses.6 Additionally, we recently developed an in
situ photochemical synthesis of chloroformates with a mixture
of CHCl3 and an aliphatic alcohol without other reagents
(reaction 3).8 Although it is known that an alcohol serves as a
stabilizer to inhibit decomposition of CHCl3,9 in situ reaction
of the alcohol and COCl2 generated through oxidative
photodecomposition of CHCl3 allowed formation of the
chloroformate in high yield. By taking advantage of using
CHCl3, which bifunctionally serves as a reactant and a solvent,
the photochemical synthesis of chloroformate was further
extended to the one-pot synthesis of carbonate esters upon
subsequent addition of an alcohol with or without an organic
base, which works as a catalyst as well as HCl scavenger.10
Since organic bases such as triethylamine and pyridine absorb
UV light,11 further difficulties were expected in the direct
photochemical synthesis of the carbonate with a CHCl3
solution containing the mixture of alcohol and organic base,
both of which inhibit the photodecomposition of CHCl3.
However, to our surprise, the reaction occurred to give the
carbonate esters (reaction 4). This new method allows a
convenient photo-on-demand phosgenation reaction that can
achieve gram-scale synthesis of the product in practical high
yield with a simple safe reaction system.
RESULTS AND DISCUSSION
■
A low-pressure mercury lamp mainly generates UV light with
wavelengths of 184.9 and 253.7 nm, and its electric power
consumption is generally low. This UV light covers the
electronic absorption bands of CHCl3 owing to σ−σ* and/or
n−σ* transitions.8b,12 The lamp (20 W, ø24 mm × 120 mm,
illuminance at distances of 5 mm: 2.00−2.33 and 5.96−8.09
mW/cm2 at 185 and 254 nm, respectively) was inserted into
the sample solution via a quartz glass jacket (ø28 mm) at the
center of a cylindrical flask (ø42 mm). Photochemical
reactions were carried out with this reaction system under
O2 bubbling (0.1 L/min) in 20−60 mL (250−750 mmol) of
CHCl3 containing 5−30 mmol of alcohol and 0.1−5.0 equiv
amounts of organic base under vigorous stirring of the sample
solution at variable temperature. The unreacted contents of the
photodecomposed gas and HCl generated by the reaction were
trapped outside with water containing a base such as NaHCO3.
With the above reaction setup, we previously reported that a
CHCl3 solution containing EtOH (20 mmol) under O2
bubbling, when exposed to the UV light at 30 °C, provided
the corresponding chloroformate, formate, and carbonate in
51%, 3%, and 4% yields, respectively.8b The reaction might
proceed through in situ reaction of the alcohol with COCl2
generated by the oxidative photodecomposition of CHCl3. In
this study, with the expectation that the carbonate ester would
be the main product, the photoreactions were conducted by
mixing 3.5 equiv amounts of pyridine in CHCl3 solutions
containing EtOH or 2-PrOH, but no products, not even
chloroformate, were obtained (Table 1, entries 1 and 2). Here,
the pyridine might inhibit the oxidative photodecomposition of
CHCl3 by absorbing UV light and/or trapping the radical
species generated from CHCl3.8b,13 This mechanism is
supported by the fact that the amount of COCl2 generated
upon oxidative photodecomposition of 30 mL of CHCl3
a
Reaction procedures and conditions: A CHCl3 solution (20−60 mL)
containing 5−30 mmol of alcohol and 0.0−5.0 equiv. amounts of
organic base under O2 bubbling (0.1 L/min) was exposed to UV-light
with a 20 W low-pressure mercury lamp at 20−30 °C for 1.0−6.5 h.
b
c
No product. The yield was determined by 1H NMR analysis.
d
Complicated product mixture.
showed a 54% decrease in the presence of 30 mmol of
pyridine.
Although phenol, with a lower nucleophilicity than alkyl
alcohols, showed no reaction without a base (entry 3), quite
interestingly, the phosgenation reaction occurred to give DPC
in 61% yield in the presence of a 3.5 equiv amount of pyridine
(entry 4). The yield was further increased by increasing the
amount of pyridine (entry 5). Phenol, having a relatively
higher acidity (pKa = 10.0)3b than alkyl alcohols (pKa = 15−
18), forms a weak complex with pyridine in the CHCl3
solution through an acid−base interaction. In fact, an
9812
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
association constant of K = 33 M−1 could be estimated by a 1H
NMR spectroscopic titration experiment (Figure S1). This
interaction may decelerate the possible radical trapping but
paradoxically accelerate the nucleophilic substitution of phenol
to COCl2 and chloroformate. When using triethylamine
(TEA) instead of pyridine, a complicated reaction mixture
was obtained, mainly owing to the photodecomposition of
TEA (entry 6). We next demonstrated the photochemical
synthesis of carbonate esters with CHCl3 solutions containing
phenol derivatives having higher acidities by attachment of
electron-withdrawing groups, and pyridine. 4-Fluorophenol
and 2-fluorophenol, having an electron-withdrawing fluorine
atom, provided the corresponding carbonate esters in 93% and
96% yields, respectively (entries 7 and 8). 4-Cyanophenol and
4-nitrophenol, having electron-withdrawing substituent groups,
also provided the carbonate esters in 62% and 39% yields,
respectively (entries 9 and 10). Furthermore, the reaction
proceeded in high yields even with pentachlorophenol and
pentafluorophenol, having lower pKa values of 4.96 and 5.53,
respectively (entries 11 and 12).14,15 2-Naphthol, having a
larger π-conjugation structure with relatively lower pKa value
(9.51) than phenol,16 also provided the corresponding
carbonate ester in >99% yield (entry 13). While a reaction
with 4-methoxyphenol, whose acidity is relatively lower (pKa =
10.05)17 than that of phenol by attachment of the electron
donating methoxy group, the corresponding carbonate ester
was also obtained in high yield (entry 14).
observed with 2,6-dichloropyridine, having lower basicity
(entry 4). 2,6-Lutidine, having higher basicity, allowed the
reaction, but the yield was decreased, probably due to the
acceleration derived from forming the HCl salt (entry 5) and
steric effects of the attached methyl groups.
Next, we extended this photochemical reaction to other
fluorinated alkyl alcohols, whose pKa is relatively higher than
that of HFIP but lower than that of alkyl alcohols.
Trifluoroethanol (pKa = 12.4)18 was converted to the
carbonate ester in 98% yield (Table 3, entry 1). 2,2,3,3,3-
Table 3. Photochemical Syntheses of Halocarbonate Esters
with CHCl3 Solutions Containing a Haloalkyl Alcohol and
a
Pyridine
With the hypothesis that the acid−base complexation
enables the in situ photochemical synthesis of carbonate esters
from the CHCl3 solution containing a mixture of alcohol and
base, we next conducted reactions with fluorinated alkyl
alcohols having relatively high acidities. For example,
1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) with a pKa value of
9.3 showed no reaction without a base (Table 2, entry 1).18
Table 2. Effects of Organic Base in the Photochemical
Synthesis of Bis(1,1,1,3,3,3-hexafluoropropan-2-yl)
a
Carbonate (BHFC)
a
Reaction procedures and conditions: A CHCl3 solution (20 mL)
containing 5−20 mmol of alcohol and 3.5−5.0 equiv. amounts of
organic base under O2 bubbling (0.1 L/min) was exposed to UV-light
with a 20 W low-pressure mercury lamp at 20−30 °C for 2.0−12.0 h.
HFIP
Time
(h)
Yield
(%)
Entry
(mmol)
Base (equiv)
b
1
2
3
4
5
20
20
20
20
20
−
−
3.0
3.0
3.0
3.0
3.0
−
b
1
The yield was determined by H NMR analysis.
c
Pyridine
Pyridine
2,6-Dichloropyridine
2,6-Lutidine
2.0
0.1
2.0
2.0
>99
c
2
−
b
Pentafluoro-1-propanol and 2,2,3,3-tetrafluoro-1-propanol,
having higher pKa values, also provided the corresponding
carbonates in 58% and >99% yields, respectively (entries 2 and
3). However, 3,3,3-trifluoro-1-propanol, whose pKa value
(14.6)18 is higher than that of the former fluorinated alcohols
but lower than that of 1-propanol, showed only 2% conversion
to the carbonate ester (entry 4). With these results, we could
then synthesize a variety of halogenated carbonates by
reference to the acidity of the alcohols. 1,1,1,3,3,3-Hexa-
fluoro-2-methyl-2-propanol and 1,1,1,3,3,3-hexafluoro-2-phe-
nyl-2-propanol, with methyl and phenyl groups, respectively,
attached to the HFIP backbone, also provided the carbonates
in 44% and 34% yields (entries 5 and 6). A highly fluorinated
alkyl carbonate could be synthesized from a CHCl3 solution of
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)pentan-3-ol in
61% yield (entry 7). The reaction was not limited to
fluorinated alcohols, but could be used for a chlorinated
c
12
a
Reaction procedures and conditions: A CHCl3 solution (20 mL)
containing 20 mmol of HFIP and 0.0−2.0 equiv. amounts of organic
base under O2 bubbling (0.1 L/min) was exposed to UV-light with a
20 W low-pressure mercury lamp at 20−30 °C for 3.0 h. No product.
The yield was determined by H NMR analysis.
b
c
1
However, it quantitatively provided the corresponding
carbonate ester in the presence of 2.0 equiv of pyridine
(entry 2). The association constant for HFIP and pyridine in
CDCl3 was actually estimated to be K = 58 M−1 in the H
1
NMR spectroscopic titration (Figure S2). The yield was
dramatically decreased when using a catalytic 0.1 equiv amount
of pyridine (entry 3). These results showed that the product
yield was highly dependent on the organic base added. With
respect to the substituent group on pyridine, no reaction was
9813
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
alcohol. Thus, bis(1,1,1,3,3,3-hexachloropropan-2-yl) carbo-
nate (BHCC) was successfully synthesized from 1,1,1,3,3,3-
hexachloro-2-propanol in 81% yield (entry 8).
X-ray crystallographic analysis of BHCC shows that it adopts
a planar W-shaped conformation with a C1−O1 bond length
of 1.194 Å and C1−O2 and C1−O3 lengths of 1.341 and
1.344 Å, respectively (Figure 1). The observed length of the
polycarbonate in quantitative yield with an average molecular
weight of Mw and Mn = 52 000 and 23 000, respectively
(reaction 2). Bisphenol AF (BPAF), having trifluoromethyl
groups, also provided a polycarbonate with Mw and Mn =
14 000 and 6400, respectively (reaction 3). An aliphatic diol,
2,2,3,3,4,4-hexafluoro-1,5-pentanediol, afforded the corre-
sponding polycarbonate with Mw and Mn = 41 300 and
24 400, respectively, in 59% yield (reaction 4).
CONCLUSION
■
In this study, we developed a novel in situ photo-on-demand
synthesis of carbonate esters with a CHCl3 solution containing
a mixture of an alcohol and an organic base. Although both the
alcohol and organic base are potential inhibitors of the
oxidative photodecomposition of CHCl3, their acid−base
interaction, which reduces the inhibitory effects, may enable
formation of COCl2 to allow in situ phosgenation reactions.
This photochemical reaction is a simple safe method of
synthesizing carbonate esters and is expected to replace current
organic syntheses using phosgene and phosgene oligomers.
EXPERIMENTAL SECTION
■
Figure 1. Single-crystal X-ray structure of BHCC. Gray, C; red, O;
green, Cl; white, H.
General Information. Unless otherwise noted, all reagents were
purchased from commercial suppliers and used without further
purification. For column chromatography, Wakogel (60N, particle size
38−100 μm, silica gel, irregular) was used. H and 13C NMR spectra
1
former CO bond is close to those reported for aliphatic
carbonate esters.19 The latter ester C−O bonds are slightly
longer (0.01−0.02 Å) than those for the reference carbonates,
likely owing to the electron-withdrawing effect of the attached
CCl3 groups. The CCl3 groups enhance the acidity of the C−H
bonds and may result in head-to-head dimerization of BHCC
molecules in the crystal packing structure through two CH−O
interactions with a C2−O1 distance of 3.141 Å.
Finally, as an application of the photochemical synthesis of
carbonate esters, we demonstrated reactions with diols. A
CHCl3 solution containing a mixture of catechol, having OH
groups on the 1- and 2-positions of the phenyl ring, and
pyridine provided a five-membered cyclic ester in >99% yield
upon photoirradiation under O2 bubbling (Scheme 2, reaction
1). Under similar conditions, bisphenol A (BPA) provided a
were recorded on Bruker AVANCE 400 spectrometer or Bruker
AVANCE 500 spectrometer, where chemical shifts (δ in ppm) were
determined with respect to tetramethylsilane as an internal standard.
19F NMR spectra were recorded on a Bruker AVANCE 400
spectrometer, where chemical shifts (δ in ppm) were determined
with respect to hexafluorobenzene as an external standard. Fourier
transform infrared spectroscopy (FT-IR) was recorded on a JASCO
FT/IR 4200. Fourier transform mass spectrometry (FT-MS) was
performed on a Thermo Fisher Scientific LTQ Orbitrap. Gas
chromatography time-of-flight mass spectrometry (GC/TOF-MS)
was performed on Agilent 7890A GC/JEOL JMS-T200 AccuTOF
GCx-plus. Elemental analysis was carried out on a Yanaco CHN
corder MT-5 analyzer. Size exclusion chromatography (SEC)
measurements were performed at 40 °C on TOHSOH TSKgel
G5000HHR and TSKgel G4000HHR columns using a JASCO Type
PU-2089 quaternary gradient pump, equipped with a JASCO Type
Scheme 2. Photochemical Syntheses of Cyclic Carbonate and Polycarbonate Esters with CHCl3 Solutions Containing a Diol
a
and Pyridine
a
Reaction procedures and conditions: A CHCl3 solution (20 mL) containing 5−10 mmol of alcohol and 5.0 equiv. amounts of pyridine under O2
bubbling (0.1 L/min) was exposed to UV-light with a 20 W low-pressure mercury lamp at 20 °C for 40−120 min.
9814
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
RI-4030 refractive index detector with THF as eluent, or on two
TOSOH TSKgel GMHHR-H columns using a TOSOH HLC-8320
GPC system equipped with a differential refractive index detector
with CHCl3 as eluent. Polystyrene standards were used in the
calibration of the molecular weights of the polymers. The single-
crystal X-ray diffraction data were collected on a Bruker APEX II
Ultra CCD diffractometer using MoKα radiation (λ = 0.71073 Å).
The data were collected at 183 K, and the structure was resolved by
direct methods and refined by full-matrix least-squares on F2
(SHELXL97). Single crystals of bis(1,1,1,3,3,3-hexachloropropan-2-
yl) carbonate (BHCC) were prepared by sublimation crystallization
in a glass tube oven (SIBATA SCIENTIFIC TECHNOLOGY, Model
GTO-1000) at 80 °C under full vacuum with an oil rotary vacuum
pump.
fluorophenyl) carbonate was obtained through recrystallization with
acetone/n-hexane as a white solid in 96% yield (0.98 g, 3.9 mmol). 1H
NMR (400 MHz, DMSO-d6, 293 K): δ 7.58 (td, J = 8.0, 1.6 Hz, 2H),
7.50−7.39 (m, 4H), 7.32 (t, J = 7.8 Hz, 2H). 13C{1H} NMR (125
MHz, CDCl3, 293 K): δ 154.9 (d, 1JC−F = 248.6 Hz), 150.4, 138.5 (d,
2JC−F = 12.9 Hz), 128.0 (d, 3JC−F = 7.4 Hz), 124.6 (d, 3JC−F = 3.8 Hz),
2
123.1, 117.1 (d, JC−F = 17.3 Hz). 19F NMR (376 MHz, CDCl3, 293
K): δ −129.06, −129.09, −129.12. IR (ATR) ν (cm−1): 3061, 2925,
2363, 1776, 1499, 1230, 752. HRMS (ESI FT-ICR) m/z: [M + H]+
Calcd for C13H9F2O3 251.0514; Found 251.0520.
Bis(4-cyanophenyl) Carbonate. CHCl3 (60 mL, 750 mmol), 4-
cyanophenol (3.6 g, 30 mmol), and pyridine (7.4 mL, 90 mmol) were
mixed in a cylindrical flask. The sample solution was stirred vigorously
with O2 bubbling (0.1 L/min) under exposure to light at 30 °C for 4
h. After the light was turned off, the sample solution was stirred at 50
°C for 2 h. It was then washed with HCl (aq., 1 M) and CH2Cl2 to
afford a light yellow solid. It was dried under vacuum to give bis(4-
cyanophenyl) carbonate as a white solid in 62% yield (2.5 g, 9.3
General Procedure for the Synthesis of Carbonate Esters. A
cylindrical flask (ø42 × 120 mm) equipped with a low-pressure
mercury lamp (SEN Light Co., UVL20PH-6, 20 W, ø24 × 120 mm)
was charged with a CHCl3 solution containing 2.5−30.0 mmol of
alcohol and 2.0−5.0 equiv amounts of organic base. Heating of the
sample solutions, if necessary, were performed with an aluminum
block bath or water bath. The sample solution was stirred vigorously
with O2 bubbling (0.1 L/min) under exposure to light at 10−30 °C
for 0.7−12.0 h. After the light was turned off, the sample solution was
stirred at 10−50 °C for 0.5−3.5 h to remove unreacted COCl2
1
mmol). H NMR (400 MHz, CDCl3, 293 K): δ 7.76 (d, J = 8.8 Hz,
4H), 7.44 (d, J = 8.8 Hz, 4H). 13C{1H} NMR (125 MHz, CDCl3, 293
K): δ 153.5, 150.2, 134.0, 121.9, 117.8, 110.8. IR (ATR) ν (cm−1):
3104, 3073, 2234, 1763, 1603, 1498, 1412, 1286, 1252, 1192, 1162,
1111, 1010, 889, 837, 819, 765, 551. HRMS (ESI FT-ICR) m/z: [M
+ Na]+ Calcd for C15H8N2O3Na 287.0427; Found 287.0428.
Bis(4-nitrophenyl) Carbonate. CHCl3 (60 mL, 750 mmol), 4-
nitrophenol (4.2 g, 30 mmol), and pyridine (7.4 mL, 90 mmol) were
mixed in a cylindrical flask. The sample solution was stirred vigorously
with O2 bubbling (0.1 L/min) under exposure to light at 30 °C for 6.5
h. After the light was turned off, the sample solution was stirred at 50
°C for 2 h. It was then washed with HCl (aq., 1 M) and extracted with
CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4 and evaporated to dryness. The residue was subjected to a
silica gel column chromatography with CH2Cl2 as an eluent to furnish
bis(4-nitrophenyl) carbonate as a light yellow solid in 39% yield (1.8
g, 5.8 mmol). 1H NMR (400 MHz, CDCl3, 293 K): δ 8.35 (d, J = 9.6
Hz, 4H), 7.50 (d, J = 9.2 Hz, 4H). 13C{1H} NMR (125 MHz, CDCl3,
293 K): δ 154.8, 150.0, 145.9, 125.5, 121.7. All 1H and 13C NMR data
are in agreement with those reported in the literature and those
recorded in the National Institute of Advanced Industrial Science and
Technology (AIST) database.20
1
generated in the solution. The product yields were determined in H
NMR spectroscopy with CH2Cl2, CHCl2CHCl2, or CH3CN as an
internal standard.
The resulting sample solution was then washed with HCl (aq., 1 M,
20 mL × 3) and extracted with CH2Cl2 (20 mL × 3). The organic
layers were combined, dried over anhydrous Na2SO4, and evaporated
to dryness. The corresponding carbonate was obtained through
recrystallization, vacuum distillation, or silica gel column chromatog-
raphy.
Diphenyl Carbonate. CHCl3 (20 mL, 250 mmol), phenol (0.94 g,
10 mmol), and pyridine (4.0 mL, 50 mmol) were mixed in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 20 °C for 1 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. It was then washed with HCl (aq., 1 M) and extracted with
CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4 and evaporated to dryness to give diphenyl carbonate as a
1
Bis(pentachlorophenyl) Carbonate. CHCl3 (20 mL, 250 mmol),
pentachlorophenol (1.3 g, 5.0 mmol), and pyridine (2.0 mL, 25
mmol) were mixed in a cylindrical flask. The sample solution was
stirred vigorously with O2 bubbling (0.1 L/min) under exposure to
light at 20 °C for 2 h. After the light was turned off, the sample
solution was stirred at 50 °C for 1 h. Methanol was added to the
sample solution to give a precipitate. It was then collected through
filtration and washed with methanol to give bis(pentachlorophenyl)
carbonate as a white solid in 72% yield (1.0 g, 1.8 mmol). 13C{1H}
NMR (100 MHz, CDCl3, 293 K): δ 143.2, 133.0, 132.5, 129.1, 127.6.
IR (ATR) ν (cm−1): 1799, 1389, 1364, 1258, 1239, 1129, 759, 711,
472, 467, 434, 420, 412. MS (ESI FT-ICR) m/z: [M]+ Calcd for
C13Cl10O3 553.6733; Found 553.6591.
white solid in >99% yield (1.1 g, 5.0 mmol). H NMR (400 MHz,
1
CDCl3, 293 K): δ 7.44−7.39 (m, 4H), 7.29−7.25 (m, 6H). All H
NMR data are in agreement with those reported in the literature.6b
Bis(4-fluorophenyl) Carbonate. CHCl3 (20 mL, 250 mmol), 4-
fluorophenol (1.1 g, 10 mmol), and pyridine (4.0 mL, 50 mmol) were
mixed in a cylindrical flask. The sample solution was stirred vigorously
with O2 bubbling (0.1 L/min) under exposure to light at 20 °C for 1
h. After the light was turned off, the sample solution was stirred at 50
°C for 1.5 h. It was then washed with HCl (aq., 1.0 M) and extracted
with CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4 and evaporated to dryness. Bis(4-fluorophenyl) carbonate
was obtained through recrystallization with acetone/n-hexane as a
1
white solid in 93% yield (0.74 g, 3.0 mmol). H NMR (400 MHz,
Bis(pentafluorophenyl) Carbonate. CHCl3 (60 mL, 750 mmol),
pentafluorophenol (5.5 g, 30 mmol), and pyridine (12 mL, 150
mmol) were mixed in a cylindrical flask. The sample solution was
stirred vigorously with O2 bubbling (0.1 L/min) under exposure to
light at 30 °C for 3 h. After the light was turned off, the sample
solution was stirred at 50 °C for 1 h. It was then washed with HCl
(aq., 1 M) and extracted with CH2Cl2. The combined organic layer
was dried over anhydrous Na2SO4 and evaporated to dryness.
Vacuum distillation of the residue with a glass tube oven provided
bis(pentachlorophenyl) carbonate as a white solid in 76% yield (4.5 g,
11 mmol). 13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 148.2, 142.2,
142.1, 141.7, 141.6, 141.5, 140.1, 140.0, 139.7, 139.6, 139.5, 139.2,
139.1, 139.0, 137.2, 137.1, 137.0, 125.3, 125.2, 125.1. 19F NMR (376
MHz, CDCl3, 293 K): δ −152.60 (d, J = 18.0 Hz, 4F), −155.21 (t, J =
23.0 Hz, 2F), −160.69 (t, J = 18.0 Hz, 4F). IR (ATR) ν (cm−1):
1810, 1657, 1519, 1474, 1321, 1224, 1152, 1048, 978, 951, 754, 742.
DMSO-d6, 293 K): δ 7.46−7.43 (m, 4H), 7.34−7.29 (m, 4H).
13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 161.5 (d, 1JC−F = 244.1
3
2
Hz), 152.2, 146.8, 122.4 (d, JC−F = 8.3 Hz), 116.4 (d, JC−F = 23.6
Hz). 19F NMR (376 MHz, DMSO-d6, 293 K): δ −116.17, −116.19,
−116.20, −116.21, −116.22, −116.23, −116.24. IR (ATR) ν (cm−1):
3649, 3121, 3083, 1764, 1505, 1279, 1176, 824. MS (ESI FT-ICR)
m/z: [M + MeOH]+ Calcd for C14H12F2O4 282.0698; Found
282.2787.
Bis(2-fluorophenyl) Carbonate. CHCl3 (20 mL, 250 mmol), 2-
fluorophenol (0.76 mL, 8.2 mmol), and pyridine (4.0 mL, 50 mmol)
were mixed in a cylindrical flask. The sample solution was stirred
vigorously with O2 bubbling (0.1 L/min) under exposure to light at
20 °C for 1 h. After the light was turned off, the sample solution was
stirred at 50 °C for 3.5 h. It was then washed with HCl (aq., 1.0 M)
and extracted with CH2Cl2. The combined organic layer was dried
over anhydrous Na2SO4 and evaporated to dryness. Bis(2-
9815
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
All 19F and 13C NMR data are in agreement with those measured with
the commercially available compound.
pyridine (5.6 mL, 70 mmol) were mixed in a cylindrical flask. The
sample solution was stirred vigorously with O2 bubbling (0.1 L/min)
under exposure to light at 20 °C for 12 h. After the light was turned
off, the sample solution was stirred at 30 °C for 2 h. 1H NMR
spectroscopy revealed that bis(2,2,3,3,3-pentafluoropropyl) carbonate
was formed in 58% yield in the sample solution. It was then washed
with HCl (aq., 1 M) and extracted with CH2Cl2. The combined
organic layer was dried over anhydrous Na2SO4. Vacuum distillation
of the residue with a glass tube oven provided bis(2,2,3,3,3-
pentafluoropropyl) carbonate as a colorless liquid in 37% yield (1.2
g, 3.7 mmol). 1H NMR (400 MHz, CDCl3, 293 K): δ 4.66 (t, J = 12.4
Hz, 4H). 13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 153.2, 116.4
Bis(naphthalen-2-yl) Carbonate. CHCl3 (20 mL, 250 mmol),
naphthalen-2-ol (1.4 g, 10 mmol), and pyridine (4.0 mL, 50 mmol)
were mixed in a cylindrical flask. The sample solution was stirred
vigorously with O2 bubbling (0.1 L/min) under exposure to light at
20 °C for 1 h. After the light was turned off, the sample solution was
stirred at 50 °C for 2.5 h. It was then washed with HCl (aq., 1.0 M)
and extracted with CH2Cl2. The combined organic layer was dried
over anhydrous Na2SO4 and evaporated to dryness. Bis(naphthalen-2-
yl) carbonate was obtained through recrystallization with acetone/n-
1
hexane as a brown solid in >99% yield (3.8 g, 5.0 mmol). H NMR
1
1
(qt, JC−F = 284.2 Hz, 2JC−F = 34.6 Hz), 109.5 (tq, JC−F = 255.0 Hz,
(400 MHz, DMSO-d6, 293 K): δ 8.07−7.97 (m, 8H), 7.63−7.55 (m,
6H). 13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 152.3, 148.6,
133.6, 131.6, 129.7, 127.8, 126.8, 126.0, 120.2, 118.0. IR (ATR) ν
(cm−1): 3052, 2363, 1763, 1509, 1288, 741. HRMS (ESI FT-ICR) m/
z: [M + Na]+ Calcd for C21H14O3Na 337.0835, Found 337.0828.
Bis(4-methoxyphenyl) Carbonate. CHCl3 (20 mL, 250 mmol), 4-
methoxyphenol (1.2 g, 10 mmol), and pyridine (4.0 mL, 50 mmol)
were mixed in a cylindrical flask. The sample solution was stirred
vigorously with O2 bubbling (0.1 L/min) under exposure to light at
20 °C for 1 h. After the light was turned off, the sample solution was
stirred at 50 °C for 2.0 h. It was then washed with HCl (aq., 1.0 M)
and extracted with CH2Cl2. The combined organic layer was dried
over anhydrous Na2SO4 and evaporated to dryness. Bis(4-
methoxyphenyl) carbonate was obtained through recrystallization
with acetone/n-hexane as a brown solid in >99% yield (1.5 g, 5.0
2
2JC−F = 38.3 Hz), 61.3 (t, JC−F = 28.3 Hz). 19F NMR (376 MHz,
CDCl3, 293 K): δ −83.86 (s, 6F), −124.00 (t, J = 12.2 Hz, 4F). IR
(ATR) ν (cm−1): 1782, 1411, 1291, 1196, 1108, 982, 764. HRMS
(ESI FT-ICR) m/z: [M + Na]+ Calcd for C7H4F10O3Na 348.9893;
Found 348.9884.
Bis(2,2,3,3-tetrafluoropropyl) Carbonate. CHCl3 (20 mL, 250
mmol), 2,2,3,3-tetrafluoropropanol (1.8 mL, 20 mmol), and pyridine
(5.6 mL, 70 mmol) were mixed in a cylindrical flask. The sample
solution was stirred vigorously with O2 bubbling (0.1 L/min) under
exposure to light at 20 °C for 5 h. After the light was turned off, the
1
sample solution was stirred at 30 °C for 2 h. H NMR spectroscopy
revealed that bis(2,2,3,3-tetrafluoropropyl) carbonate was formed in
>99% yield in the sample solution. It was then washed with HCl (aq.,
1 M) and extracted with CH2Cl2. The combined organic layer was
dried over anhydrous Na2SO4. Vacuum distillation of the residue with
a glass tube oven provided bis(2,2,3,3-tetrafluoropropyl) carbonate as
a colorless liquid in 88% yield (2.5 g, 8.8 mmol). 1H NMR (400 MHz,
CDCl3, 293 K): δ 5.91 (tt, J = 53.2, 3.8 Hz, 2H), 4.59 (tt, J = 12.6, 1.2
Hz, 4H). 13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 153.5, 113.8
1
mmol). H NMR (400 MHz, CDCl3, 293 K): δ 7.19 (d, J = 8.8 Hz,
4H), 6.92 (d, J = 9.2 Hz, 4H), 3.81 (s, 6H). 13C{1H} NMR (125
MHz, CDCl3, 293 K): δ 157.5, 152.8, 144.7, 121.8, 114.5, 55.6. IR
(ATR) ν (cm−1): 3069, 2359, 1767, 1506, 1175, 1028, 828. HRMS
(ESI FT-ICR) m/z: [M + H]+ Calcd for C15H15O5 275.0914, Found
275.0914.
1
2
1
(tt, JC−F = 220.4 Hz, JC−F = 28.3 Hz), 109.4 (tt, JC−F = 248.6 Hz,
Bis(1,1,1,3,3,3-hexafluoropropan-2-yl) Carbonate. CHCl3 (20
mL, 250 mmol), 1,1,1,3,3,3-hexafluoro-2-propanol (2.1 mL, 20
mmol), and pyridine (3.2 mL, 40 mmol) were mixed in a cylindrical
flask. The sample solution was stirred vigorously with O2 bubbling
(0.1 L/min) under exposure to light at 10 °C for 3 h. After the light
2JC−F = 36.5 Hz), 63.7 (t, JC−F = 29.1 Hz). 19F NMR (376 MHz,
2
CDCl3, 293 K): δ −124.26 (s, 4F), −137.71 (d, J = 50.4 Hz, 4F). IR
(ATR) ν (cm−1): 2985, 1774, 1446, 1406, 1272, 1202, 1100, 1013,
986, 837, 782. HRMS (ESI FT-ICR) m/z: [M + Na]+ Calcd for
C7H6F8O3Na 313.0081; Found 313.0076.
1
was turned off, the sample solution was stirred at 10 °C for 1 h. H
Bis(3,3,3-trifluoropropyl) Carbonate. CHCl3 (20 mL, 250 mmol),
3,3,3-trifluoropropanol (1.8 mL, 20 mmol), and pyridine (5.6 mL, 70
mmol) were mixed in a cylindrical flask. The sample solution was
stirred vigorously with O2 bubbling (0.1 L/min) under exposure to
light at 20 °C for 3 h. After the light was turned off, the sample
solution was stirred at 30 °C for 2 h. 1H NMR spectroscopy revealed
that bis(3,3,3-trifluoropropyl) carbonate was formed in 2% yield in
the sample solution. 1H NMR (400 MHz, CDCl3, 293 K): δ 4.38 (t, J
= 6.6 Hz, 4H), 2.59−2.48 (m, 4H). 13C{1H} NMR (125 MHz,
NMR spectroscopy revealed that bis(1,1,1,3,3,3-hexafluoropropan-2-
yl) carbonate was formed in >99% yield in the sample solution. It was
then subjected to atmospheric distillation at 65−78 °C to obtain a
colorless liquid separated into two layers. The bottom layer was
separated to give bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate as a
colorless liquid in 45% yield (1.6 g, 4.5 mmol). 1H NMR (400 MHz,
CDCl3, 293 K): δ 5.56 (sep, J = 5.6 Hz, 2H). 13C{1H} NMR (125
MHz, CDCl3, 293 K): δ 151.7, 120.9 (q, 1JC−F = 280.0 Hz), 71.9 (sep,
2JC−F = 35.5 Hz). 19F NMR (376 MHz, CDCl3, 293 K): δ −73.81(s,
12F). IR (ATR) ν (cm−1): 2987, 1806, 1795, 1384, 1369, 1295, 1254,
1200, 1163, 1114, 1061, 1003, 911, 896, 872, 772, 762, 736, 686. All
1H and 19F NMR data are in agreement with those reported in the
literature.21
CDCl3, 293 K): δ 154.4, 125.6 (q, 1JC−F = 274.1 Hz), 61.0 (d, 3JC−F
=
3.8 Hz), 33.4 (q, 2JC−F = 29.1 Hz). 19F NMR (376 MHz, CDCl3, 293
K): δ −65.13 (s, 6F). IR (ATR) ν (cm−1): 2927, 1750, 1392, 1351,
1294, 1255, 1162, 1010, 850, 671. HRMS (ESI FT-ICR) m/z: [M +
Na]+ Calcd for C7H8F6O3Na 277.0270; Found 277.0265.
Bis(2,2,2-trifluoroethyl) Carbonate. CHCl3 (20 mL, 250 mmol),
2,2,2-trifluoroethanol (0.71 mL, 10 mmol), and pyridine (4.0 mL, 50
mmol) were mixed in a cylindrical flask. The sample solution was
stirred vigorously with O2 bubbling (0.1 L/min) under exposure to
light at 20 °C for 2 h. After the light was turned off, the sample
solution was stirred at 50 °C for 1 h. 1H NMR spectroscopy revealed
that bis(2,2,2-trifluoroethyl) carbonate was formed in 98% yield in the
sample solution. It was then washed with HCl (aq., 1 M) and
extracted with CH2Cl2. The combined organic layer was dried over
anhydrous Na2SO4. Atmospheric distillation of the sample solution
afforded bis(2,2,2-trifluoroethyl) carbonate as a colorless liquid in
46% yield (0.52 g, 2.3 mmol). 1H NMR (400 MHz, CDCl3, 293 K): δ
4.58 (q, J = 8.0 Hz, 4H). 13C{1H} NMR (125 MHz, CDCl3, 293 K):
Bis(1,1,1,3,3,3-hexafluoro-2-methyl-2-propyl) Carbonate. CHCl3
(20 mL, 250 mmol), 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (2.3
mL, 19 mmol), and pyridine (5.3 mL, 65 mmol) were mixed in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 20 °C for 4.5 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. It was then washed with HCl (aq., 1 M) and extracted with
CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4. Vacuum distillation of the residue with a glass tube oven
provided bis(1,1,1,3,3,3-hexafluoro-2-methyl-2-propyl) carbonate as a
colorless liquid in 44% yield (1.6 g, 4.1 mmol). 1H NMR (400 MHz,
CDCl3, 293 K): δ 2.00 (s, 6H). 13C{1H} NMR (125 MHz, CDCl3,
1
2
1
2
δ 153.2, 122.3 (q, JC−F = 276.0 Hz), 64.3 (q, JC−F = 37.4 Hz). 19F
293 K): δ 146.8, 121.5 (q, JC−F = 283.3 Hz), 82.1 (q, JC−F = 31.9
Hz), 13.6. 19F NMR (376 MHz, CDCl3, 293 K): δ −76.35 (s, 12F).
IR (ATR) ν (cm−1): 1807, 1459, 1397, 1305, 1227, 1165, 1111, 1087,
1043, 915, 719, 695. HRMS (ESI FT-ICR) m/z: [M]+ Calcd for
C9H6F12O3 390.0125; Found 390.0125.
NMR (376 MHz, CDCl3, 293 K): δ −74.29 (s, 6F). All H and 19F
1
NMR data are in agreement with those reported in the literature.22
Bis(2,2,3,3,3-pentafluoropropyl) Carbonate. CHCl3 (20 mL, 250
mmol), 2,2,3,3,3-pentafluoropropanol (2.0 mL, 20 mmol), and
9816
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
Bis(1,1,1,3,3,3-hexafluoro-2-phenyl-2-propyl) Carbonate. CHCl3
(20 mL, 250 mmol), 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol (3.4
mL, 20 mmol), and pyridine (5.6 mL, 70 mmol) were mixed in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 20 °C for 7 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. It was then washed with HCl (aq., 1M) and extracted with CH2Cl2.
The combined organic layer was dried over anhydrous Na2SO4.
Vacuum distillation of the residue with a glass tube oven provided
bis(1,1,1,3,3,3-hexafluoro-2-phenyl-2-propyl) carbonate as a white
Benzo[1,3]dioxol-2-one. CHCl3 (20 mL, 250 mmol), catechol (1.1
g, 10 mmol), and pyridine (4.0 mL, 50 mmol) were mixed in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 20 °C for 2 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. It was then washed with HCl (aq., 1 M) and extracted with
CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4 and evaporated to dryness to leave a yellow solid. It was
further recrystallized with n-hexane to afford benzo[1,3]dioxol-2-one
as a white solid in >99% yield (1.3 g, 10 mmol). 1H NMR (400 MHz,
CDCl3, 293 K): δ 7.30−7.23 (m, 4H). 13C{1H} NMR (125 MHz,
1
solid in 34% yield (1.8 g, 3.4 mmol). H NMR (400 MHz, CDCl3,
1
CDCl3, 293 K): δ 151.2, 143.3, 124.9, 110.5. All H and 13C NMR
293 K): δ 7.51−7.43 (m, 10H). 13C{1H} NMR (125 MHz, CDCl3,
data are in agreement with those reported in the literature.23
1
293 K): δ 145.9, 130.8, 128.8, 126.4, 126.0, 121.2 (q, JC−F = 287.9
Hz), 84.7 (t, 2JC−F = 30.0 Hz). 19F NMR (376 MHz, CDCl3, 293 K):
δ −70.27 (s, 12F). IR (ATR) ν (cm−1): 1814, 1276, 1242, 1226,
1199, 1176, 1153, 1113, 1087, 1044, 1028, 1011, 984, 949, 916, 756,
737, 712, 696, 661. HRMS (ESI FT-ICR) m/z: [M + Na]+ Calcd for
C19H10F12O3Na 537.0331; Found 537.0312.
Polycarbonate from BPA. CHCl3 (20 mL, 250 mmol), bisphenol
A (BPA) (2.3 g, 10 mmol), and pyridine (4.0 mL, 50 mmol) were
mixed in a cylindrical flask. The sample solution was stirred vigorously
with O2 bubbling (0.1 L/min) under exposure to light at 20 °C for 40
min. After the light was turned off, the sample solution was stirred at
50 °C for 1 h. Methanol was added to the sample solution to give a
precipitate. It was then collected through filtration and washed with
methanol to give polycarbonate as a white solid in >99% yield (2.7 g,
Bis(1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)pentan-3-yl)
Carbonate. NaBH4 (3.0 g, 80 mmol) was added slowly to a mixture
solution of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-penta-
none (32 g, 100 mmol) in 35 mL of tetraethylene glycol dimethyl
ether at 0 °C. The mixture was then vigorously stirred at 0 °C for 1.5
h. The sample solution was washed with HCl (aq., 1M) and extracted
with Novec7100. The combined organic layer was dried over
anhydrous Na2SO4. Vacuum distillation of the residue with a glass
tube oven provided 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)
pentanol as a colorless liquid.
1
11 mmol). H NMR (400 MHz, CDCl3, 293 K): δ 7.25 (d, J = 8.4
Hz, 4H), 7.16 (d, J = 8.8 Hz, 4H), 1.68 (s, 6H). 13C{1H} NMR (125
MHz, CDCl3, 293 K): δ 152.2, 148.9, 148.3, 127.9, 120.3, 42.6, 30.9.
All 1H and 13C NMR data are in agreement with those reported in the
literature.24
Polycarbonate from BPAF. CHCl3 (20 mL, 250 mmol), 2,2-bis(4-
hydroxyphenyl) hexafluoropropane (BPAF) (1.7 g, 5.0 mmol), and
pyridine (2.0 mL, 25 mmol) were mixed in a cylindrical flask. The
sample solution was stirred vigorously with O2 bubbling (0.1 L/min)
under exposure to light at 20 °C for 2 h. After the light was turned off,
the sample solution was stirred at 50 °C for 1 h. Methanol was added
to the sample solution to give a precipitate. It was then collected
through filtration and washed with methanol to give polycarbonate as
CHCl3 (20 mL, 250 mmol), 1,1,1,2,2,4,5,5,5-nonafluoro-4-
(trifluoromethyl) pentanol (3.2 g, 10 mmol), and pyridine (4.0 mL,
50 mmol) were mixed in a cylindrical flask. The sample solution was
stirred vigorously with O2 bubbling (0.1 L/min) under exposure to
light at 30 °C for 2 h. After the light was turned off, the sample
solution was stirred at 50 °C for 0.5 h. Vacuum distillation of the
sample solution with a glass tube oven provided bis(1,1,1,2,2,4,5,5,5-
nonafluoro-4-(trifluoromethyl)pentan-3-yl) carbonate as a colorless
1
a white solid in >99% yield (2.1 g, 5.0 mmol). H NMR (400 MHz,
CDCl3, 293 K): δ 7.47 (d, J = 8.0 Hz, 4H), 7.33 (d, J = 8.4 Hz, 4H).
13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 156.2, 151.2, 131.7,
131.3, 127.5, 123.9 (t, 1JC−F = 286.0 Hz), 115.1, 64.0 (t, 2JC−F = 26.4
Hz). 19F NMR (376 MHz, CDCl3, 293 K): δ −63.87 (s, 6F). All 1H,
13C, and 19F NMR data are in agreement with those reported in the
literature.25
1
liquid in 61% yield (2.0 g, 3.1 mmol). H NMR (400 MHz, CDCl3,
293 K): δ 5.99 (dt, J = 18.0, 4.8 Hz, 2H). 13C{1H} NMR (125 MHz,
CDCl3, 293 K): δ 150.5, 123.0, 122.8, 122.6, 122.4, 120.7, 120.5,
120.3, 120.1, 119.1, 118.8, 118.6, 118.5, 118.2, 118.0, 117.8, 116.8,
116.6, 116.3, 114.3, 112.5, 112.2, 110.4, 110.3, 110.0, 110.0, 108.2,
107.9, 90.3, 90.1, 89.8, 88.6, 88.3, 88.0, 70.7, 70.2, 70.0, 69.8, 69.8,
69.6, 69.6, 69.4. 19F NMR (376 MHz, CDCl3, 293 K): δ −72.28,
−75,73, −83.15, −119.82, −124.84, −182.64. IR (ATR) ν (cm−1):
1812, 1336, 1303, 1203, 1173, 1105, 1058, 1014, 975, 954, 768, 730,
696, 685. HRMS (ESI FT-ICR) m/z: [M − F]+ Calcd for
C13H2F23O3 642.9631; Found 642.9613.
Polycarbonate from 2,2,3,3,4,4-Hexafluoro-1,5-pentanediol.
CHCl3 (20 mL, 250 mmol), 2,2,3,3,4,4-hexafluoro-1,5-pentanediol
(1.1 g, 5.0 mmol), and pyridine (2.0 mL, 25 mmol) were mixed in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 20 °C for 2 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. Acetone and methanol were added to the sample solution to give a
precipitate. It was then collected through filtration, and washed with
methanol to give polycarbonate as a light yellow solid in 59% yield
Bis(1,1,1,3,3,3-hexachloropropan-2-yl) Carbonate. NaBH4 (1.28
g, 34 mmol) was added slowly to a tert-butyl alcohol solution (68 mL)
containing hexachloroacetone (10.4 mL, 68 mmol) at room
temperature and vigorously stirred for 27 h. The sample solution
was filtered to remove precipitate and evaporated to dryness. Vacuum
distillation of the residue with a glass tube oven provided 1,1,1,3,3,3-
hexachloropropan-2-yl as a white solid.
The obtained sample (1.34 g, 5.0 mmol) was then mixed with
pyridine (1.4 mL, 18 mmol) in CHCl3 (20 mL, 250 mmol) in a
cylindrical flask. The sample solution was stirred vigorously with O2
bubbling (0.1 L/min) under exposure to light at 30 °C for 3 h. After
the light was turned off, the sample solution was stirred at 50 °C for 1
h. It was then washed with HCl (aq., 1 M) and extracted with
CH2Cl2. The combined organic layer was dried over anhydrous
Na2SO4 and evaporated to dryness. The residue was subjected to a
silica gel column chromatography with CH2Cl2 as an eluent to furnish
bis(1,1,1,3,3,3-hexachloropropan-2-yl) carbonate as a white solid in
81% yield (1.1 g, 2.0 mmol). 1H NMR (400 MHz, CDCl3, 293 K): δ
6.07 (s, 2H). 13C{1H} NMR (125 MHz, CDCl3, 293 K): δ 152.3,
94.3, 88.2. IR (ATR) ν (cm−1): 2982, 2961, 1786, 1323, 1238, 984,
860, 822, 610. HRMS (ESI FT-ICR) m/z: [M + Na]+ Calcd for
C7H2Cl12O3Na 576.6158; Found 576.6148.
1
(0.70 g, 3.0 mmol). H NMR (400 MHz, DMSO-d6, 293 K): δ 4.94
(t, J = 11.0 Hz, 4H); 13C{1H} NMR (125 MHz, DMSO-d6, 293 K): δ
1
2
1
152.6, 114.3 (tt, JC−F = 255 Hz, JC−F = 30.0 Hz), 110.5 (tt, JC−F
=
262.4 Hz, 2JC−F = 31.9 Hz), 63.1 (t, 2JC−F = 25.5 Hz). 19F NMR (376
MHz, DMSO-d6, 293 K): δ −119.72 (s, 4F), −125.34 (s, 2F). IR
(ATR) ν (cm−1): 2979, 1768, 1447, 1413, 1268, 1209, 1153, 1113,
1022, 992, 961, 895, 781, 760. Anal. Calcd for [C7H6F6O3]n: C, 30.27;
H, 1.69. Found: C, 30.24; H, 1.69.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.1c01210.
1H, 13C{1H}, and 19F NMR spectra; crystallographic
data; GPC profiles (PDF)
Accession Codes
CCDC 2067452 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
9817
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
D.; Hedrick, J. L.; Ong, Z. Y.; Yang, Y. Y.; Sardon, H. Non-Isocyanate
Polyurethane Soft Nanoparticles Obtained by Surfactant-Assisted
Interfacial Polymerization. Langmuir 2017, 33, 1959−1968. (g) Su-
giyama, M.; Akiyama, M.; Nishiyama, K.; Okazoe, T.; Nozaki, K.
Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as
a Carbonyl Source. ChemSusChem 2020, 13, 1775−1784.
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
■
(3) (a) Chen, W.; Li, K. A New Method for Synthesizing
Asymmetric Urea Containing Thiazolo[5,4-b]pyridine And Applica-
tions in Agriculture. Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186,
311−318. (b) Kamps, J. H.; Hoeks, T.; Kung, K.; Lens, J. P.;
McCloskey, P. J.; Noordover, B. A. J.; Heuts, J. P. A. Activated
Carbonates: Enabling the Synthesis of Differentiated Polycarbonate
resins via melt transcarbonation. Polym. Chem. 2016, 7, 5294−5303.
(c) Baral, E. R.; Lee, J. H.; Kim, J. G. Diphenyl Carbonate: A Highly
Reactive and Green Carbonyl Source for the Synthesis of Cyclic
Carbonates. J. Org. Chem. 2018, 83, 11768−11776. (d) Dobi, Z.;
Reddy, B. N.; Renders, E.; Van Raemdonck, L.; Mensch, C.; De Smet,
G.; Chen, C.; Bheeter, C.; Sergeyev, S.; Herrebout, W. A.; Maes, B. U.
W. Carbamate Synthesis Using a Shelf-Stable and Renewable C1
Reactant. ChemSusChem 2019, 12, 3103−3114. (e) Zhang, Z.; Xu, F.;
Zhang, Y.; Li, C.; He, H.; Yang, Z.; Li, Z. A Non-phosgene Process for
Bioderived Polycarbonate with High Molecular Weight and Advanced
Property Profile Synthesized Using Amino Acid Ionic Liquids as
Catalysts. Green Chem. 2020, 22, 2534−2542. (f) Yakeya, D.; Yoshida,
Y.; Endo, T. Phosgene-free and Chemoselective Synthesis of Novel
Polyureas from Activated L-Lysine with Diphenyl Carbonate.
Macromolecules 2020, 53, 6809−6815.
(4) Fukuoka, S.; Fukawa, I.; Adachi, T.; Fujita, H.; Sugiyama, N.;
Sawa, T. Industrialization and Expansion of Green Sustainable
Chemical Process: A Review of Non-phosgene Polycarbonate from
CO2. Org. Process Res. Dev. 2019, 23, 145−169.
(5) Shirota, N.; Okazoe, T.; Kashiwagi, K. (Asahi Glass Co., Ltd.).
WO 2014/171367A1, 2014.
(6) (a) Tsuda, A. (Kobe University). JP 2013181028A, 2013.
(b) Kuwahara, Y.; Zhang, A.; Soma, H.; Tsuda, A. Photochemical
Molecular Storage of Cl2, HCl, and COCl2: Synthesis of Organo-
chlorine Compounds, Salts, Ureas, and Polycarbonate with Photo-
decomposed Chloroform. Org. Lett. 2012, 14, 3376−3379. (c) Zhang,
A.; Kuwahara, Y.; Hotta, Y.; Tsuda, A. Organic Syntheses with
Photochemically Generated Chemicals from Tetrachloroethylene.
Asian J. Org. Chem. 2013, 2, 572−578.
Akihiko Tsuda − Department of Chemistry, Graduate School
of Science, Kobe University, Kobe 657-8501, Japan;
orcid.org/0000-0002-9232-1455; Email: tsuda@
harbor.kobe-u.ac.jp
Authors
Yuka Hashimoto − Department of Chemistry, Graduate
School of Science, Kobe University, Kobe 657-8501, Japan
Sasuga Hosokawa − Department of Chemistry, Graduate
School of Science, Kobe University, Kobe 657-8501, Japan
Fengying Liang − Department of Chemistry, Graduate School
of Science, Kobe University, Kobe 657-8501, Japan
Yuto Suzuki − Department of Chemistry, Graduate School of
Science, Kobe University, Kobe 657-8501, Japan
Namin Dai − Department of Chemistry, Graduate School of
Science, Kobe University, Kobe 657-8501, Japan
Gegen Tana − Department of Chemistry, Graduate School of
Science, Kobe University, Kobe 657-8501, Japan
Kazuo Eda − Department of Chemistry, Graduate School of
Science, Kobe University, Kobe 657-8501, Japan;
orcid.org/0000-0001-8741-6874
Toshifumi Kakiuchi − Innovative Technology Laboratories,
AGC Inc., Yokohama City, Kanagawa 230-0045, Japan
Takashi Okazoe − Materials Integration Laboratories, AGC
Inc., Yokohama City, Kanagawa 230-0045, Japan
Hidefumi Harada − Tokyo Research Laboratory, Mitsubishi
Gas Chemical Company, Inc., Katsushika-ku, Tokyo 125-
8601, Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.1c01210
(7) (a) Tsuda, A. (National University Corporation Kobe
University, AGC Inc.). WO 2018211953A1, 2018. (b) Tsuda, A.
(National University Corporation Kobe University, Mitsubishi Gas
Chemical Company, Inc.). WO 2018211952A1, 2018.
(8) (a) Tsuda, A. (National University Corporation Kobe
University). WO 2015156245A1, 2015. (b) Liang, F.; Yanai, M.;
Suzuki, Y.; Tsuda, A. Photo-on-Demand Synthesis of Chloroformates
with a Chloroform Solution Containing an Alcohol and Its One-Pot
Conversion to Carbonates and Carbamates. Org. Lett. 2020, 22,
3566−3569.
(9) (a) Baskerville, C.; Hamor, W. A. The Chemistry of
Anaesthetics, IV: Chloroform. J. Ind. Eng. Chem. 1912, 4 (212),
278−288, 362−372, 422−429, 499−506, and 571−578. (b) Kawai, S.
Discussion on Decomposition of Chloroform. Yakugaku Zasshi 1966,
86, 1125−1132. (c) Riddick, J. A.; Bunger, W. B. Techniques of
Chemistry, Vol. II; Organic Solvents; Wiley: New York, 1970; pp
771−773.
(10) (a) Kirzecky, N. D.; Thomson, M. L.; Wayne, R. S. Acid
Chloride to Ester Formation: Mechanism of SO2-Amine Interference.
J. Org. Chem. 1987, 52, 3452−3455. (b) Nie, J.; Shen, J.; Shim, Y. Y.;
Tse, T. J.; Reaney, M. J. T. Synthesis of Trimethylolpropane Esters by
Base-Catalyzed Transesterification. Eur. J. Lipid Sci. Technol. 2020,
122, 1900207.
Notes
The authors declare the following competing financial
interest(s): This research was funded by AGC Inc. and
Mitsubishi Gas Chemical Company, Inc.
ACKNOWLEDGMENTS
■
This research was supported by the Adaptable and Seamless
Technology Transfer Program through Target-driven R&D
(A-STEP), Seeds development type from Japan Science and
Technology Agency (JST).
REFERENCES
■
(1) Cotarca, L.; Eckert, H. Phosgenations-A Handbook; Wiley-VCH:
Weinheim, 2003.
(2) (a) He, X.-S.; Brossi, A. DI-(2,2,2-Trichloroethyl)-Carbonate:
Byproduct in Reactions with 2,2,2-Trichloroethyl Chloroformate.
Synth. Commun. 1990, 20, 2177−2179. (b) Mori, K. (Central Glass
Co., Ltd.), JP 2000319230A, Nov 21, 2000. (c) Okazoe, T.;
Okamoto, H.; Tajima, K.; Nagasaki, Y. (Asahi Glass Co., Ltd.).
WO 2010001870A1, 2010. (d) Okazoe, T.; Nagasaki, Y.; Okamoto,
H. (Asahi Glass Co., Ltd.). WO 2011125429, 2010. (e) Bogolubsky,
A. V.; Moroz, Y. S.; Mykhailiuk, P. K.; Granat, D. S.; Pipko, S. E.;
Konovets, A. I.; Doroschuk, R.; Tolmachev, A. Bis(2,2,2-trifluor-
oethyl) Carbonate as a Condensing Agent in One-Pot Parallel
Synthesis of Unsymmetrical Aliphatic Ureas. ACS Comb. Sci. 2014,
16, 303−308. (f) Bossion, A.; Jones, G. O.; Taton, D.; Mecerreyes,
(11) (a) Ohkuma, S.; Sakai, I. Detection of Aromatic Primary
Amines by a Photochemical Reaction with Pyridine. Bunseki Kagaku
1975, 24, 385−387. (b) Mercier, P.; Dupuis, P.; Sauvageau, P.;
Sandorfy, C. The Electronic Spectrum of the Triethylamine-perfluoro-
tert-butanol Complex. Chem. Phys. Lett. 1979, 68, 1−4. (c) Prather, K.
9818
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
A.; Lee, Y. T. The Photodissociation of Pyridine at 193 nm. Isr. J.
Chem. 1994, 34, 43−53. (d) Errami, M.; El Dib, G.; Cazaunau, M.;
Roth, E.; Salghi, R.; Mellouki, A.; Chakir, A. Atmospheric
Degradation of Pyridine: UV Absorption Spectrum and Reaction
with OH Radicals and O3. Chem. Phys. Lett. 2016, 662, 141−145.
(12) (a) Russell, B. R.; Edwards, L. O.; Raymonda, J. W. Vacuum
Ultraviolet Absorption Spectra of the Chloromethanes. J. Am. Chem.
Soc. 1973, 95, 2129−2133. (b) Ogita, T.; Hatta, H.; Kagiya, T.
Photoinduced Decomposition of Trihalomethanes in Aqueous
Solution by UV Irradiation. Nippon Kagaku Kaishi 1983, 11, 1664−
1669.
(13) Elsayed, M. A. Successive Advanced Oxidation of Pyridine by
Ultrasonic Irradiation: Effect of Additives and Kinetic Study. Desalin.
Water Treat. 2015, 53, 57−65.
(14) Schaller, K. H.; Valentin, H. The MAK-Collection for
Occupational Health and Safety; Wiley-VCH: Weinheim, 2012; pp
217−235.
(15) Kutt, A.; Leito, I.; Kaljurand, I.; Sooväli, L.; Vlasov, V. M.;
̈
Yagupolskii, L. M.; Koppel, I. A. A Comprehensive Self-Consistent
Spectrophotometric Acidity Scale of Neutral Brønsted Acids in
Acetonitrile. J. Org. Chem. 2006, 71, 2829−2838.
(16) Bhattacharyya, D.; Hamrin, C. E.; Northey, R. P. Oxidation of
Hazardous Organics in a Two-Phase Fluorocarbon-Water System.
Hazard. Waste Hazard. Mater. 1986, 3 (3), 405−429.
(17) Slater, B.; McCormack, A.; Avdeef, A.; Comer, J. PH-Metric
logP.4. Comparison of Partition Coefficients Determined by HPLC
and Potentiometric Methods to Literature Values. J. Pharm. Sci. 1994,
83, 1280−1283.
(18) (a) Mihailovic, M. L.; Cekovic, Z. The Chemistry of the Hydroxyl
Group; Patai, S., Ed.; Wiley-Interscience: New York, 1971; Vol. 1, p
506. (b) Ouellett, R. J.; Rawn, J. D. Organic Chemistry: Structure,
Mechanism, and Synthesis, 2nd ed.; Academic Press: United Kingdom,
2018; p 274.
(19) (a) Evans, D. A.; Kozlowski, M. C.; Murry, J. A.; Burgey, C. S.;
Campos, K. R.; Connell, B. T.; Staples, R. J. C2-Symmetric Copper(II)
Complexes as Chiral Lewis Acids. Scope and Mechanism of Catalytic
Enantioselective Aldol Additions of Enolsilanes to (Benzyloxy)-
acetaldehyde. J. Am. Chem. Soc. 1999, 121, 669−685. (b) Kino, R.;
Daikai, K.; Kawanami, T.; Furuno, H.; Inanaga, J. Remarkable Effect
of Tris(4-fluorophenyl)phosphine Oxide on the Stabilization of Chiral
Lanthanum Complex Catalysts. A New and Practical Protocol for the
Highly Enantioselective Epoxidation of Conjugated Enones. Org.
Biomol. Chem. 2004, 2, 1822−1824. (c) Ajayi, K.; Thakur, V. V.;
Lapo, R. C.; Knapp, S. Intramolecular I-Glucosaminidation: Synthesis
of Mycothiol. Org. Lett. 2010, 12, 2630−2633.
(20) (a) Dong, Z.; Li, X.; Liang, K.; Mao, S.; Huang, X.; Yang, B.;
Xu, J.; Liu, J.; Luo, G.; Shen, J. Telluroxides Exhibit Hydrolysis
Capacity. J. Org. Chem. 2007, 72, 606−609. (b) SDBS-12570. 1H and
13C NMR spectra, RN 5070-13-3; National Institute of Advanced
Industrial Science and Technology (AIST) database.
(21) Matsuura, K.; Kashiwagi, K.; Okazoe, T. (AGC Inc.). Japanese
Patent 2014−208595 A, 2014.
(22) Krespan, C. G.; Smart, B. E. Fluorocarbanion Chemistry. A
Versatile Synthesis of Functionalized Fluoro Ketones. J. Org. Chem.
1986, 51, 320−326.
(23) Baral, E. R.; Lee, J. H.; Kim, J. G. Diphenyl Carbonate: A
Highly Reactive and Green Carbonyl Source for the Synthesis of
Cyclic Carbonates. J. Org. Chem. 2018, 83, 11768−11776.
(24) Saladino, M. L.; Armetta, F.; Sibeko, M. A.; Luyt, A. S.; Chillura
Martino, D. F.; Caponetti, E. Preparation and Characterisation of
Ce:YAG -polycarbonate Composites for White LED. J. Alloys Compd.
2016, 664, 726−731.
(25) Cai, Z.; Yu, H.; Zhang, Y.; Li, M.; Niu, X.; Shi, Z.; Cui, Z.;
Chen, C.; Zhang, D. Synthesis and Characterization of Novel
Fluorinated Polycarbonate Negative-type Photoresist for Optical
Waveguide. Polymer 2015, 61, 140−146.
9819
https://doi.org/10.1021/acs.joc.1c01210
J. Org. Chem. 2021, 86, 9811−9819