Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату
Pentafluorophenyl iodine(III) diacetate (F5-PIDA) is an electron-deficient hypervalent iodine(III) reagent with growing utility in modern synthetic methodology, including iodine(III)-mediated ring-expansion chemistry. However, its application as a stoichiometric reagent requires reliable access to p...
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Репозитарії
Journal of Organic and Pharmaceutical Chemistry| _version_ | 1867660261862670336 |
|---|---|
| author | Sham, Vadim Borysov , Oleksandr V. |
| author_facet | Sham, Vadim Borysov , Oleksandr V. |
| author_institution_txt_mv | [
{
"author": "Vadim Sham",
"institution": "Institute of Organic Chemistry of the National Academy of Sciences of Ukraine; Enamine Ltd"
},
{
"author": "Oleksandr V. Borysov ",
"institution": "Institute of Organic Chemistry of the National Academy of Sciences of Ukraine; Enamine Ltd"
}
] |
| author_sort | Sham, Vadim |
| baseUrl_str | https://ophcj.nuph.edu.ua/oai |
| collection | OJS |
| datestamp_date | 2026-06-10T08:24:31Z |
| description | Pentafluorophenyl iodine(III) diacetate (F5-PIDA) is an electron-deficient hypervalent iodine(III) reagent with growing utility in modern synthetic methodology, including iodine(III)-mediated ring-expansion chemistry. However, its application as a stoichiometric reagent requires reliable access to preparative amounts. This article describes a practical chromatography-free protocol for the preparation of F5-PIDA on a ca. 300 g scale by the oxidation of pentafluoroiodobenzene with sodium hypochlorite pentahydrate in acetic acid. The product was isolated by a simple slurry trituration in the hexane/MTBE mixture giving F5-PIDA in the yield of 65% and the purity of ≥ 98%. The thermogravimetry-differential thermal analysis has shown that F5-PIDA is stable up to approximately 100-110 °C, while the rapid decomposition occurs above this temperature range. The protocol developed provides a reliable preparative access to high-purity F5-PIDA and practical thermal data for its safe use. |
| doi_str_mv | 10.24959/ophcj.26.361529 |
| first_indexed | 2026-06-11T01:00:23Z |
| format | Article |
| fulltext |
ISSN 2308-8303 (Print) / 2518-1548 (Online) 3
Technical Note
http://ophcj.nuph.edu.ua
UDC 547.1:547.22:547.66
V. Sham1,2, O. V. Borysov1,2
1 Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
5 Academician Kukhar str., 02094 Kyiv, Ukraine
2 Enamine Ltd, 78, Winston Churchill str., 02094 Kyiv, Ukraine
A Scalable Preparation and Thermal Analysis
of Pentafluorophenyl Iodine(III) Diacetate
Abstract
Pentafluorophenyl iodine(III) diacetate (F5-PIDA) is an electron-deficient hypervalent iodine(III) reagent with growing utility
in modern synthetic methodology, including iodine(III)-mediated ring-expansion chemistry. However, its application as a stoichio-
metric reagent requires reliable access to preparative amounts. This article describes a practical chromatography-free proto-
col for the preparation of F5-PIDA on a ca. 300 g scale by the oxidation of pentafluoroiodobenzene with sodium hypochlorite
pentahydrate in acetic acid. The product was isolated by a simple slurry trituration in the hexane/MTBE mixture giving F5-PIDA
in the yield of 65 % and the purity of ≥ 98 %. The thermogravimetry-differential thermal analysis has shown that F5-PIDA is
stable up to approximately 100 – 110 °C, while the rapid decomposition occurs above this temperature range. The protocol
developed provides a reliable preparative access to high-purity F5-PIDA and practical thermal data for its safe use.
Keywords: hypervalent iodine; λ3-iodane; scale-up; semi-industrial method; F5-PIDA
В. Шам1,2, О. В. Борисов1,2
1 Інститут органічної хімії Національної академії наук України,
вул. Академіка Кухаря, 5, м. Київ, 02660, Україна
2 ТОВ НВП «Єнамін», вул. Вінстона Черчилля, 78, м. Київ, 02094, Україна
Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату
Анотація
Пентафлуорофенілйод(III) діацетат (F5-PIDA) є електронодефіцитним реагентом йоду(III), що набуває дедалі більшого
значення в сучасній синтетичній методології, зокрема в реакціях розширення циклу. Однак його застосування як сте-
хіометричного реагенту потребує надійного доступу до препаративних його кількостей. У цій роботі описано практич-
ний протокол одержання F5-PIDA в масштабі ca. 300 г шляхом окиснення пентафлуоройодобензену натрій гіпохлоритом
пентагідратом в оцтовій кислоті без використання хроматографічного очищення. Продукт було виділено шляхом про-
стої тритурації в суміші гексан/MTBE з виходом 65 % і чистотою ≥ 98 %. Термогравіметричний / диференційно-термічний
аналіз показав, що F5-PIDA є стабільним без суттєвої втрати маси до приблизно 100 – 110 °C, тоді як вище цього тем-
пературного діапазону відбувається швидкий розклад. Розроблений протокол забезпечує надійний препаративний
доступ до високочистого F5-PIDA і надає практичні термічні дані для його безпечного використання.
Ключові слова: гіпервалентний йод; λ3-йодан; масштабування; напівіндустріальний метод; F5-PIDA
Citation: Sham, V.; Borysov, O. V. A Scalable Preparation and Thermal Analysis of Pentafluorophenyl Iodine(III) Diacetate.
Journal of Organic and Pharmaceutical Chemistry 2026, 24 (2), 3 – 7.
https://doi.org/10.24959/ophcj.26.361529
Received: 1 March 2026; Revised: 3 May 2026; Accepted: 9 May 2026
Copyright© 2026, V. Sham, O. V. Borysov. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0).
Funding: The authors received no specific funding for this work.
Conflict of interests: The authors have no conflict of interests to declare.
ISSN 2308-8303 (Print) / 2518-1548 (Online) 4
Журнал органічної та фармацевтичної хімії 2026, 24 (2)
■ Introduction
Hypervalent iodine(III) reagents have become
important tools in modern organic synthesis since
they combine a strong oxidizing ability with ope-
rational simplicity, broad functional-group tole-
rance, and metal-free reaction conditions [1 – 3].
A recent comprehensive review reveals them as
unique reagents enabling transformations that
cannot be performed by using any other common,
non-iodine-based chemical [1]. According to the re-
view, [bis(acyloxy)iodo]arenes constitute a highly
important family of hypervalent iodine reagents,
which broad synthetic utility has been extensi-
vely covered in numerous review articles [4 – 6].
Among them, (diacetoxyiodo)arenes, ArI(OAc)2,
are especially useful oxidants and electrophilic
group-transfer reagents, and their reactivity can
be tuned by changing the electronic nature of the
aryl substituent attached to the iodine(III) center.
Notably, SciFinder® returns over 2,400 publica-
tions describing synthetic applications of the
parent reagent, (diacetoxyiodo)benzene (PIDA,
PhI(OAc)2), that appeared between 2016 and 2025.
Electron-deficient aryl iodine(III) reagents are of
particular interest as they can effectively tune
the reactivity profile of the common PIDA rea-
gent [7 – 10]. In this regard, pentafluorophenyl
iodine(III) diacetate (C6F5I(OAc)2, F5-PIDA) rep-
resents a useful fluorinated analog of PIDA, in
which the strongly electron-withdrawing penta-
fluorophenyl group increases the electrophilic cha-
racter of the iodine(III) center. This feature can
be decisive in transformations where the electro-
nic properties of the hypervalent iodine reagent
control the reaction pathway. A recent example
is the iodine(III)-mediated ring expansion of ex-
ocyclic alkenes to saturated gem-difluorinated
rings [11]. In this study, tuning the electronic
properties of the aryl iodine(III) reagent was
shown to be critical, and electron-rich analogs fa-
vored the undesired vicinal difluorination, while
electron-poor reagents promoted the desired ring-
expansion pathway. F5-PIDA was identified as
the optimal reagent, enabling an efficient forma-
tion of saturated gem-F2-rings and suppressing
competing side processes. This result highlight-
ed the synthetic value of F5-PIDA and created
a practical need for the reliable access to this
reagent in preparative quantities.
The synthesis of F5-PIDA from pentafluoro-
iodobenzene using sodium hypochlorite penta-
hydrate in acetic acid was previously reported
by Watanabe and co-workers as part of a general
safer protocol for the preparation of (diacetoxy-
iodo)arenes [12]. The method is attractive since
NaClO· 5H2O is an inexpensive, nonexplosive
oxidant and avoids the use of hazardous oxidants,
such as peracetic acid or chromium-based sys-
tems. However, the preparation of F5-PIDA in that
work was demonstrated only on a 2 mmol scale,
giving approximately 0.7 g of the product.
For a broader synthetic use, especially in re-
actions where F5-PIDA is required as a stoichio-
metric reagent, the sub-gram access is insuffi-
cient. A practical scale-up must address not only
the conversion, but also operational safety, re-
producibility, product isolation, and avoidance
of the chromatographic purification. Herein, we
describe a reproducible chromatography-free
preparation of high-purity F5-PIDA on a ca. 300 g
scale from pentafluoroiodobenzene using so-
dium hypochlorite pentahydrate as an oxidant.
In addition, the thermogravimetric analysis of
the material obtained is presented to determine
its thermal stability profile and provide practi-
cal guidance for handling this reagent on a pre-
parative scale.
■ Results and discussion
The oxidation of pentafluoroiodobenzene to
F5-PIDA was selected as the target transforma-
tion for scale-up studies. The original procedure
reported by Watanabe and co-workers [12] de-
monstrated that sodium hypochlorite pentahy-
drate is an efficient and relatively safe oxidant
for the conversion of a broad range of iodoarenes
into the corresponding (diacetoxyiodo)arenes. In
that work, pentafluoroiodobenzene was success-
fully oxidized on a 2 mmol scale to give F5-PIDA
in high purity. However, larger-scale prepara-
tion was demonstrated only for the parent PIDA
derived from iodobenzene. Therefore, direct ex-
trapolation to multihundred-gram quantities of
F5-PIDA required additional practical validation.
At the outset, we aimed to preserve the sim-
plicity of the original oxidation system while
adapting it for the preparative-scale operation.
Sodium hypochlorite pentahydrate was chosen
as the oxidant since it provides a high effective
concentration of active hypochlorite and avoids
the large excess of water associated with aque-
ous sodium hypochlorite solutions. This feature
is particularly important as aqueous hypochlo-
rite can promote the overoxidation to iodine(V)
species in related systems [12]. Acetic acid was
retained as both the reaction medium and the
ISSN 2308-8303 (Print) / 2518-1548 (Online) 5
Journal of Organic and Pharmaceutical Chemistry 2026, 24 (2)
acetate source, enabling a direct formation of the
diacetoxyiodo product.
On scale-up, several operational parameters
were adjusted (Scheme 1). Instead of adding pen-
tafluoroiodobenzene in one portion, it was intro-
duced gradually to a stirred suspension of sodium
hypochlorite pentahydrate in acetic acid. This mo-
dification provided better control over mixing and
the local reagent concentration. The reaction time
was also slightly extended relative to the small-
scale procedure to ensure the complete conver-
sion under preparative conditions. After the com-
pletion of the oxidation, the reaction mixture was
diluted with dichloromethane, and the inorganic
residues were removed by the filtration. The or-
ganic phase was dried and concentrated to give
a crude product.
A key practical issue was the isolation of
F5-PIDA in high purity without the chromato-
graphic purification or additional chemical treat-
ment. In the general procedure previously re-
ported, the purification of some (diacetoxyiodo)-
arenes could involve the recrystallization, treat-
ment with acetic anhydride, or other post-reaction
operations. For the multihundred-gram synthe-
sis, these options are less convenient. We found
that simple slurry trituration of the crude mate-
rial in the hexane/MTBE mixture (9:1) was suf-
ficient to remove impurities and give F5-PIDA as
a white solid with the purity of ≥ 98 %, as deter-
mined by the GC-MS and NMR analysis. This pu-
rification was operationally simple and avoided
the need for the column chromatography. Under
these conditions, F5-PIDA was obtained repro-
ducibly in the isolated yield of 62 – 65 % as an
analytically pure solid suitable for further syn-
thetic use.
Under the optimized preparative conditions,
pentafluoroiodobenzene was converted to F5-PIDA
on a ca. 300 g scale in a single run. The target
reagent was isolated as a white crystalline solid
weighing 273.2 g, corresponding to the yield of
65 %. The product identity was confirmed by 1H,
13C, and 19F NMR spectroscopy and the GC-MS
analysis. The material obtained was suitable for
further synthetic use, including iodine(III)-
mediated ring-expansion reactions of exocyclic al-
kenes to saturated gem-difluorinated rings, for
which F5-PIDA had previously been identified
as the optimal reagent [11].
The thermal behavior of the isolated F5-PIDA
was examined by the TG/DTA/DTG analysis in
the temperature range from room temperature to
500 °C (Figure 1). The TG curve showed no signi-
ficant mass loss below approximately 100 – 110 °C,
indicating the absence of substantial amounts of
volatile impurities or a residual solvent and sug-
gesting that the material can be handled at am-
bient temperature without a detectable thermal
degradation. A rapid mass loss began at appro-
ximately 120 – 130 °C, followed by the main de-
composition event in the range of 130 – 190 °C.
The DTG curve displayed a sharp maximum at
approximately 150 – 160 °C, corresponding to the
highest rate of the mass loss. The DTA signal
showed a thermal event in the same tempera-
ture region, consistent with the rapid decom-
position of the hypervalent iodine(III) reagent.
Above 200 °C, only a slow additional decrease in
mass was observed, and the final residue at 500 °C
accounted for approximately 1 – 3 % of the initial
sample mass. The data show that F5-PIDA pos-
sesses a defined thermal stability window but un-
dergoes the rapid decomposition shortly after the
onset temperature. Although the reagent is suf-
ficiently stable for routine handling and storage
under appropriate conditions, exposure to elevated
temperatures should be avoided during drying,
concentration, storage, or further synthetic use.
■ Conclusion
A practical protocol for the multihundred-gram
synthesis of pentafluorophenyl iodine(III) diace-
tate (F5-PIDA) has been developed. The oxidation
of 300 g of pentafluoroiodobenzene with sodium
hypochlorite pentahydrate in acetic acid gave
273.2 g of F5-PIDA, with the isolated yield of 65 %
and the purity of ≥ 98 %, as determined by the
GC-MS and NMR analysis. The procedure avoids
NaClO 5H2O
I
F
F
F
F
F F
F
F
F
F
I
AcO OAc
AcOH, rt
F5-PIDA
scale-up to 300 gca.
65 % isolated yield
purity 98 %≥
chromatography-free
isolation protocol
Scheme 1. The synthetic outline and distinct features of the protocol
ISSN 2308-8303 (Print) / 2518-1548 (Online) 6
Журнал органічної та фармацевтичної хімії 2026, 24 (2)
the chromatographic purification and relies on
a simple slurry trituration in hexane/MTBE,
making it convenient for the preparative-scale use.
The preparation of sodium hypochlorite penta-
hydrate is also included to standardize the over-
all protocol and improve the reproducibility of the
oxidation step. The TG/DTA/DTG analysis has
shown that F5-PIDA is stable without a signifi-
cant mass loss up to approximately 100 – 110 °C,
while the rapid decomposition occurs above this
range, with the main mass-loss event between
approximately 130 and 190 °C. These results pro-
vide practical guidance for handling and process-
ing the reagent.
■ Experimental part
All regents used were taken from Enamine Ltd
stock. Analytical TLC was performed using Poly-
chrom SI F254 plates. 1H and 13C NMR spectra
were recorded on a Bruker 170 AVANCE 500 in-
strument (500 MHz for 1H and 126 MHz for 13C),
19F NMR spectra were obtained on a Varian Uni-
ty Plus 400 (376 MHz) spectrometer. GCMS ana-
lyses were performed using an Agilent 5890 Se-
ries II 5972 GCMS instrument [electron impact
(EI) ionization (70 eV)], respectively.
The Preparation of Sodium Hypochlorite
Pentahydrate (NaClO·5H2O)
Caution: Chlorine is a toxic and corrosive
gas. All operations involving chlorine were per-
formed in a well-functioning fume hood using the
appropriate gas-handling and scrubbing equip-
ment. Sodium hypochlorite pentahydrate is a strong
oxidant and should be handled with the appropri-
ate protective equipment, avoiding contact with
organic materials, acids, reducing agents, and heat.
Sodium hydroxide (500 g) was dissolved in
water to prepare a 45 wt% aqueous NaOH solu-
tion (1.11 kg total). The solution was placed in
a polypropylene reactor equipped with efficient
mechanical stirring and external cooling. Chlorine
gas was introduced at a controlled rate while main-
taining the internal temperature at 25 – 30 °C.
The amount of chlorine introduced correspond-
ed to approximately 429 g of Cl2.
After the completion of the chlorine addition,
the resulting suspension was filtered through
a polypropylene frit to remove precipitated so-
dium chloride. The filtrate was transferred to
a polypropylene vessel, cooled to 12 °C, seeded
with sodium hypochlorite pentahydrate from the
previous preparation (ca. 4 g), and maintained at
this temperature for 2 days. The crystals formed
were collected by the filtration and stored at 4 °C.
The first preparation performed without seed-
ing gave a significantly lower yield. The second
crystallization of the mother liquor was also pos-
sible. However, the resulting material showed
lower activity and reduced stability. Therefore, to
prepare F5-PIDA, freshly crystallized first-crop
sodium hypochlorite pentahydrate was used.
The remaining mother liquor was used in other
oxidative transformations. This preparation was
Figure 1. The TG/DTA/DTG analysis of F5-PIDA
ISSN 2308-8303 (Print) / 2518-1548 (Online) 7
Journal of Organic and Pharmaceutical Chemistry 2026, 24 (2)
adapted from the reported patent procedure for
crystalline sodium hypochlorite pentahydrate [13].
The Preparation of Pentafluorophenyl
Iodine(III) Diacetate (F5-PIDA) on a 300 g
Scale
A suspension of sodium hypochlorite penta-
hydrate (NaClO· 5H2O, 415.8 g, 2.00 equiv)
in glacial acetic acid (2.50 L) was prepared in
a glass reactor equipped with mechanical stirring.
Pentafluoroiodobenzene (300.0 g, 1.00 equiv.)
was added over 10 min at room temperature.
The reaction mixture was stirred at room tem-
perature for approximately 15 min and then di-
luted with dichloromethane (3.0 L). The inorganic
material was removed by the filtration, and the
organic phase was dried over anhydrous Na2SO4,
filtered, and concentrated under reduced pres-
sure. The resulting crude solid was triturated
with hexane/MTBE (9:1) to give pentafluorophe-
nyl iodine(III) diacetate (F5-PIDA) as a white
solid with the purity of ≥ 98 %, as determined by
GC-MS and NMR.
A white solid. Yield – 273.2 g (65 %). M. p.
98 – 99 °C. 1H NMR (500 MHz, CDCl3), δ, ppm: 2.00
(s, 6H). 13C NMR (126 MHz, CDCl3), δ, ppm: 178.4,
146.9 – 146.5 (m), 146.2 – 145.3 (m), 144.9 – 144.4
(m), 144.1 – 143.4 (m), 138.6 – 138.1 (m), 136.6 – 136.1
(m), 96.2 (dt, J = 27.1, 4.7 Hz), 20.1. 19F NMR
(376 MHz, CDCl3), δ, ppm: -121.5 (m), -144.1 (m),
-157.0 (m). GCMS, m/z (EI): 293.9 [M-2Ac]+.
■ References
1. Yoshimura, A.; Zhdankin, V. V. Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents. Chem. Rev. 2024, 124 (19),
11108 – 11186. https://doi.org/10.1021/acs.chemrev.4c00303.
2. Zhdankin, V. V. Hypervalent iodine compounds: reagents of the future. ARKIVOC 2020, 2020 (4), 1 – 11.
https://doi.org/10.24820/ark.5550190.p011.145.
3. Macara, J.; Caldeira, C.; Poeira, D. L.; Marques, M. M. B. Reactivity of Hypervalent Iodine(III) Reagents Bearing Transferable N-Based
Groups. Eur. J. Org. Chem. 2023, 26 (25), e202300109. https://doi.org/10.1002/ejoc.202300109.
4. Vittal, S.; Mujahid Alam, M.; Hussien, M.; Amanullah, M.; Pisal, P. M.; Ravi, V. Applications of Phenyliodine(III)diacetate in C−H Functionalization
and Hetero-Hetero Bond Formations: A Septennial Update. ChemistrySelect 2023, 8 (1), e202204240. https://doi.org/10.1002/slct.202204240.
5. Alam, M. M.; Hari Babu, B.; Mohammed, A.; Mohamed, H.; Ravi, V. Phenyliodine(III)diacetate (PIDA): Applications in Rearrangement/
Migration Reactions. Curr. Org. Chem. 2023, 27 (2), 93 – 107. http://dx.doi.org/10.2174/1385272827666230330105241.
6. Varala, R.; Seema, V.; Dubasi, N. Phenyliodine(III)diacetate (PIDA): Applications in Organic Synthesis. Organics 2023, 4, 1 – 40.
https://doi.org/10.3390/org4010001.
7. Rocaboy, C.; Gladysz, J. A. Convenient Syntheses of Fluorous Aryl Iodides and Hypervalent Iodine Compounds: ArI(L)n Reagents That
Are Recoverable by Simple Liquid/Liquid Biphase Workups, and Applications in Oxidations of Hydroquinones. Chem. Eur. J. 2003, 9 (1),
88 – 95. https://doi.org/10.1002/chem.200390034.
8. Matsuzaki, K.; Okuyama, K.; Tokunaga, E.; Shiro, M.; Shibata, N. Sterically Demanding Unsymmetrical Diaryl-λ3-iodanes for Electrophilic
Pentafluorophenylation and an Approach to α-Pentafluorophenyl Carbonyl Compounds with an All-Carbon Stereocenter. ChemistryOpen
2014, 3 (6), 233 – 237. https://doi.org/10.1002/open.201402045.
9. Harayama, Y.; Yoshida, M.; Kamimura, D.; Wada, Y.; Kita, Y. The Efficient Direct Synthesis of N,O-Acetal Compounds as Key Intermediates
of Discorhabdin A: Oxidative Fragmentation Reaction of α-Amino Acids or β-Amino Alcohols by Using Hypervalent Iodine(III) Reagents.
Chem. Eur. J. 2006, 12 (18), 4893 – 4899. https://doi.org/10.1002/chem.200501635.
10. Moriarty, R. M.; Penmasta, R.; Awasthi, A. K.; Prakash, I. Mild oxidative cleavage of alkynes using [bis(trifluoroacetoxy)iodo]pentafluoroben-
zene. J. Org. Chem. 1988, 53 (26), 6124 – 6125. https://doi.org/10.1021/jo00261a031.
11. Li, Y.; Liu, X.-B.; Sham, V.; Logvinenko, I.; Xue, J.-H.; Wu, J.-Y.; Fu, J.-L.; Lin, S.; Liu, Y.; Li, Q.; Mykhailiuk, P. K.; Wang, H. Saturated F2-Rings
from Alkenes. Angew. Chem. Int. Ed. 2025, 64 (14), e202422899. https://doi.org/10.1002/anie.202422899.
12. Watanabe, A.; Miyamoto, K.; Okada, T.; Asawa, T.; Uchiyama, M. Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite
Pentahydrate. J. Org. Chem. 2018, 83 (23), 14262 – 14268. https://doi.org/10.1021/acs.joc.8b02541.
13. Tomotake, A.; Tokuji, T.; Yoshimi, I. (Nippon Light Metal Co). Method for producing sodium hypochlorite pentahydrate. JP Patent 4211130B2,
21.01.2009.
Information about the authors:
Vadim Sham, Ph.D. Student of the Institute of Organic Chemistry; Head of the Laboratory at Enamine Ltd.;
https://orcid.org/0000-0003-0059-4876.
Oleksandr V. Borysov (corresponding author), Ph.D. in Chemistry, Senior Researcher of the Institute of Organic Chemistry,
National Academy of Sciences of Ukraine; Production Manager at Enamine Ltd.; https://orcid.org/0000-0003-0360-9295.
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| spelling | oai:ojs.journals.uran.ua:article-3615292026-06-10T08:24:31Z A Scalable Preparation and Thermal Analysis of Pentafluorophenyl Iodine(III) Diacetate Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату Sham, Vadim Borysov , Oleksandr V. hypervalent iodine λ3-iodane scale-up semi-industrial method F5-PIDA гіпервалентний йод λ3-йодан масштабування напівіндустріальний метод F5-PIDA Pentafluorophenyl iodine(III) diacetate (F5-PIDA) is an electron-deficient hypervalent iodine(III) reagent with growing utility in modern synthetic methodology, including iodine(III)-mediated ring-expansion chemistry. However, its application as a stoichiometric reagent requires reliable access to preparative amounts. This article describes a practical chromatography-free protocol for the preparation of F5-PIDA on a ca. 300 g scale by the oxidation of pentafluoroiodobenzene with sodium hypochlorite pentahydrate in acetic acid. The product was isolated by a simple slurry trituration in the hexane/MTBE mixture giving F5-PIDA in the yield of 65% and the purity of ≥ 98%. The thermogravimetry-differential thermal analysis has shown that F5-PIDA is stable up to approximately 100-110 °C, while the rapid decomposition occurs above this temperature range. The protocol developed provides a reliable preparative access to high-purity F5-PIDA and practical thermal data for its safe use. Пентафлуорофенілйод(III) діацетат (F5-PIDA) є електронодефіцитним реагентом йоду(III), що набуває дедалі більшого значення в сучасній синтетичній методології, зокрема в реакціях розширення циклу. Однак його застосування як стехіометричного реагенту потребує надійного доступу до препаративних його кількостей. У цій роботі описано практичний протокол одержання F5-PIDA в масштабі ca. 300 г шляхом окиснення пентафлуоройодобензену натрій гіпохлоритом пентагідратом в оцтовій кислоті без використання хроматографічного очищення. Продукт було виділено шляхом простої тритурації в суміші гексан/MTBE з виходом 65% і чистотою ≥ 98%. Термогравіметричний / диференційно-термічний аналіз показав, що F5-PIDA є стабільним без суттєвої втрати маси до приблизно 100-110 °C, тоді як вище цього температурного діапазону відбувається швидкий розклад. Розроблений протокол забезпечує надійний препаративний доступ до високочистого F5-PIDA і надає практичні термічні дані для його безпечного використання. National University of Pharmacy 2026-06-10 Article Article Peer-reviewed Article application/pdf https://ophcj.nuph.edu.ua/article/view/361529 10.24959/ophcj.26.361529 Journal of Organic and Pharmaceutical Chemistry; Vol. 24 No. 2 (2026): Issue in Progress; 3-7 Журнал органической и фармацевтической химии; Том 24 № 2 (2026): Issue in Progress; 3-7 Журнал органічної та фармацевтичної хімії; Том 24 № 2 (2026): Issue in Progress; 3-7 2518-1548 2308-8303 en https://ophcj.nuph.edu.ua/article/view/361529/349719 Copyright (c) 2026 National University of Pharmacy http://creativecommons.org/licenses/by/4.0 |
| spellingShingle | гіпервалентний йод λ3-йодан масштабування напівіндустріальний метод F5-PIDA Sham, Vadim Borysov , Oleksandr V. Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title | Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title_alt | A Scalable Preparation and Thermal Analysis of Pentafluorophenyl Iodine(III) Diacetate |
| title_full | Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title_fullStr | Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title_full_unstemmed | Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title_short | Масштабований синтез і термічний аналіз пентафлуорофенілйод(III) діацетату |
| title_sort | масштабований синтез і термічний аналіз пентафлуорофенілйод(iii) діацетату |
| topic | гіпервалентний йод λ3-йодан масштабування напівіндустріальний метод F5-PIDA |
| topic_facet | hypervalent iodine λ3-iodane scale-up semi-industrial method F5-PIDA гіпервалентний йод λ3-йодан масштабування напівіндустріальний метод F5-PIDA |
| url | https://ophcj.nuph.edu.ua/article/view/361529 |
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