Hydroxy- and alkoxymethylation of polyfluoroalkyl pyrazoles

Article abstract of DOI:10.1007/s11172-018-2104-9

A synthetic route to 1-hydroxy- and 1-alkoxymethyl-3-polyfluoroalkylpyrazoles via regioselective N-hydroxy- and alkoxymethylation of N-unsubstituted pyrazoles with paraformaldehyde has been proposed. The alkoxyalkylation of polyfluoroalkylpyrazoles procee

Full text of DOI:10.1007/s11172-018-2104-9

Russian Chemical Bulletin, International Edition, Vol. 67, No. 3, pp. 521—524, March, 2018
521
Hydroxy- and alkoxymethylation of polyfluoroalkyl pyrazoles*
А. Е. Ivanova, E. V. Shchegol´kov, Ya. V. Burgart, and V. I. Saloutin
Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22/20 ul. S. Kovalevskoi, 620990 Ekaterinburg, Russian Federation.
E-mail: saloutin@ios.uran.ru
A synthetic route to 1-hydroxy- and 1-alkoxymethyl-3-polyfluoroalkylpyrazoles via regi-
oselective N-hydroxy- and alkoxymethylation of N-unsubstituted pyrazoles with paraformal-
dehyde has been proposed. The alkoxyalkylation of polyfluoroalkylpyrazoles proceeds in
aqueous-alcohol medium, whereas hydroxymethylation requires anhydrous conditions.
Key words: polyfluoroalkylpyrazoles, paraformaldehyde, N-hydroxy- and alkoxymethylation,
regioselectivity.
The enormous data on biological properties of pyr-
azoles allows one to designate them as promising objects
for the modification that opens the way to obtain bioactive
molecules.1—8 This is the cause of an inexhaustible inter-
est of chemists to the synthesis and modification of pyr-
azoles. According to the SciFinder® search system, more
than 40 reviews on synthesis and properties of pyrazoles
and their derivatives have been published only during the
last five years.
a previously described procedure 24 in methylene chloride
in the absence of an acid afford 1-hydroxymethylsubsti-
tuted compounds 2а—с in 5 days (Scheme 1). However,
in absolute ethanol saturated with dried hydrogen chloride,
Scheme 1
Fluorinated pyrazoles deserve special attention because
of their potential use in pharmacy and agrochemistry. Due
to unique properties of the fluorine atom,9,10 fluorinated
derivatives display distinctive physico-chemical and bio-
logical properties making them promising molecules for
formulating novel medical preparations or special-purpose
materials.10—16 Thus, a series of known medicines and
agrochemicals comprise (trifluoromethyl)pyrazole moi-
ety.17 Among them, an anti-inflammatory drug celebrex
(celecoxib), veterinary antiarthritic drug mavacoxib (trocoxil),
as well as anticoagulant preparation razaxaban18 being
currently under clinical investigation, fungicide pentiopi-
rad,19 and herbicide fluazolat20 are worth mentioning.
Here, we have studied the possibility to modify poly-
fluorinated pyrazoles 1 via reactions with paraformalde-
hyde. Non-fluorinated 1-hydroxymethylpyrazoles21,22
obtained in result of such transformations were used as
building blocks to construct acyclic nucleosides,23 various
ligands, and metal complexes including those promising
for practical applications, e.g., ZnII complexes of N,N-bis-
(1H-pyrazolyl-1-methyl)arylamines showing high catalytic
activity in polymerization of methylacrylate.24
i. CH2Cl2,  or abs. EtOH, HCl gas, ; ii. R3OH, HCl,
80—90 C.
Compound
1a,2a
RF
CF3
R1
R2
Products
R3
Et
Me 4-MeC6H4N=N
3a
4a
5a
—
—
3d
Bun
Hex
—
It was found that reac tions of polyfluoroalkylpyrazoles
1а—с with paraformaldehyde carried out according to
1b, 2b
1c, 2c
1d
CF3
H(CF2)2 Ph
C3F7
Ph
H
H
—
Et
Me 4-MeOC6H4N=N
* Dedicated to Academician of the Russian Academy of Sciences
I. P. Beletskaya.
R
4 = CH2Ph, CH2CO2H
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0521—0524, March, 2018.
1066-5285/18/6703-0521 © 2018 Springer Science+Business Media, Inc.

522
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
Ivanova et al.
F(1)
F(2)
C(11)
F(3)
C(10)
C(2)
C(12)
C(9)
N(4)
C(3)
C(4)
N(2)
N(1)
C(7)
O(1)
C(15)
C(14)
C(8)
C(13)
N(3)
C(5)
C(1)
C(6)
Fig. 1. General view of a molecule of 3a.
these reactions proceed far more rapidly (in 4 h), accord-
ing to the TLC data, and in nearly quantitative yields.
Compounds 2a—c are unstable and decompose to give
starting pyrazoles 1a—c during purification by column
chromatography.
capable of reacting with electrophilic reagents to give two
regioisomeric 3-RF- and 5-RF-pyrazoles. Actually, as
we have demonstrated earlier, methylation26 and alkyl-
ation27,28 of pyrazoles 1 proceed on both centers with
predomination of a particular isomer depending on the
reaction conditions, however, melting the pyrazoles to-
gether with (2-acetoxyethoxy)methylacetate,28 as well as
ribosylation29 proceeds regioselectively on the N(1) center.
We have found that hydroxy- and alkoxymethylation
of polyfluoroalkylpyrazoles 1 with paraformaldehyde
proceed regioselectively on the N(1) atom to give 3-RF-
pyrazoles 2а—с, 3а,d, 4a, and 5a. In this case, when
studying the reaction mixture by the GC-MS, the forma-
tion of an alternative 5-RF-isomer was not observed.
Regioisomeric structure of pyrazoles 2а—с, 3а,d, 4a, and
5a was detected by the 19F NMR spectroscopy data. Thus,
in their 19F NMR spectra, the CF3 signals were observed
in the same region (F  99.3—100.0), as those for the
starting pyrazoles 1a,b (F  99.6—100.3); similarly, the
signals of the fluorine atoms of -CF2 groups in products
3с (F 48.6) and 3d (F 52.2) were observed in the same
regions as those for N-unsubstituted pyrazoles 1с (F 48.9)
and 1d (F 52.3).
For pyrazole 3a, X-ray diffraction analysis has been per-
formed, also confirming its 3-CF3-isomeric structure (Fig. 1).
Regioselectivity of the reactions under consideration
may result from the preferable existence of pyrazoles 1 in
a tautomeric form with a "pyrrole" nitrogen atom at a non-
fluorinated substituent.26 As a result, an addition of form-
aldehyde proceeds on the N(1) atom affording 1-hydroxy-
methyl-3-RF-pyrazoles 2. The latter can eliminate the OH
group in an aqueous acid forming an intermediate carbo-
cation A, which adds to an alcohol to yield 1-alkoxymethyl-
ated pyrazoles 3—5 (Scheme 2).
Further, we have investigated the possibility of amino-
methylation of polyfluoroalkyl pyrazoles 1 via the Mannich
reaction with paraformaldehyde and amines. A hetero-
cycle having the NH-center is known to act in these reac-
tions either as a substrate capable of reacting with para-
formaldehyde or as an amine component.25 First, we
proposed that pyrazoles 1 can act as substrates. However,
it turned out that 4-aryldiazenylpyrazole 1а reacting with
benzylamine, taken as an amine component, remains
unchanged under the classical Mannich reaction condi-
tions (acidic catalysis, ethanol), whereas reaction with
glycine under the same conditions produces 3-trifluoro-
methyl-1-ethoxymethylpyrazole 3а rather than an expected
N-aminomethyl pyrazole 6 (see Scheme 1). Changing the
reaction conditions, namely, replacement a solvent for
acetonitrile, did not produce an aminomethylation prod-
uct. The molecule of a solvent (ethanol) seemed to act as
a substrate when forming the product 3a, whereas pyrazole
1a reacted as an amine component. Ethoxymethylation of
pyrazole 1d was carried out in refluxing EtOH with para-
formaldehyde in the presence of hydrochloric acid without
an amine, thus affording pyrazole 3d. Moderate yields in
these reactions are defined by an incomplete conversion
of the substrate. Prolonging the reaction time resulted in
the formation of unidentifiable mixtures.
By the example of reactions of 4-aryldiazenylpyrazole
1а with butanol and hexanol it was shown that alkoxy-
methylation discovered by us can be applied to obtain other
1-alkoxymethylpyrazoles 4а and 5а (see Scheme 1). Here,
as the alcohol carbon chain length increases, the reaction
time is reduced, and the product yields are improved.
Unsymmetrical polyfluoroalkylpyrazoles 1 have two
competitive nucleophilic centers, namely, N(1) and N(2),
To summarize, we have discovered the reaction of
regioselective N-alkoxymethylation of polyfluoroalkyl
pyrazoles with paraformaldehyde in an aqueous-alcoholic
medium, whereas under absolute (anhydrous) conditions

Hydroxy(alkoxy)methylation of fluoropyrazoles
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
523
Scheme 2
Table 1. Crystallographic data and X-ray data for com-
pound 3a*
Parameter
3a
Formule
С15Н17F3N4О
326.32
Triclinic
P–1
Molecular weight
Syngony
Space group
a/Å
8.966(11)
10.390(5)
10.623(11)
110.55(7)
100.54(9)
110.82(7)
810.7(13)
2
b/Å
c/Å
/deg
/deg
/deg
V/Å3
Z
dcalc/g cm–3
1.337
the reaction is terminated at the step of 1-hydroxymethyl-
ated pyrazole formation.
/mm–1
0.950
Total number of reflections
Number of independent reflections
R1-factor
9004
2742
Experimental
0.062
The number of refined parameters
211
IR spectra were recorded on a «Perkin Elmer Spectrum One»
IR-Fourier spectrometer in 4000–400 cm–1 range using Atten-
uated Total Reflection technique. NMR spectra were recorded
on a Bruker DRX-400 spectrometer (1Н, 400 MHz, relatively
SiMe4, 19F, 376 MHz, relatively С6F6) and on a Bruker
Avance-500 spectrometer (1Н, 500 MHz, relatively SiMe4, 19F,
470 MHz, relatively С6F6), using CDCl3 as the main solvent,
unless noted otherwise. Elemental analyses (C, H, N) were
performed using an elemental analyzer Perkin Elmer PE 2400,
series II. Melting points were measured in opened capillaries on
a Stuart SMP30 apparatus. Column chromatography was per-
formed on a silica gel, grade 60 (0.063—0.2 mm), supplied by
Alfa Aesar.
Single crystals of pyrazole 3a were obtained by crystallization
from chloroform. X-ray studies were performed on a Xcalibur 3
automatic diffractometer equipped with a CCD-detector (graph-
ite monochromator, (Cu-К) = 1.54184 Å, /-scan technique,
temperature 295(2) К). The absorption correction was done
analytically using a multifaceted crystal model on a CrysAlis RED
1.171.29.9 software. Crystal structures were solved by direct
method and refined by the full matrix least square method on F2
using the SHELXTL software package.30 Non-hydrogen atoms
were refined in anisotropic approximation; hydrogen atoms were
placed in geometrically calculated positions and included into
the refinement using a rider model with dependent isotropic
thermal parameters.
* Complete crystallographic data for compound 3a are
available on https://www.ccdc.cam.ac.uk/structures
(CCDC 1586571).
1180—1250 (C—F). NMR 1Н,  2.61 (s, 3 Н, 5-Me); 3.88 (s, 3 Н,
ОMe); 6.97—7.00 (m, 2 Н, Hm, С6Н4); 7.79—7.81 (m, 2 Н, Ho,
С6Н4). NMR 19F, : 35.55 (m, 2 F, -CF2); 52.30 (m, 2 F,
-CF2); 81.5 (t, 3 F, CF3, J = 9.4 Hz). Found (%): С, 43.88;
Н, 2.75; N, 14.36. С14Н11F7N4О. Calculated (%): С, 43.76;
Н, 2.89; N, 14.58.
Synthesis of 1-hydroxymethyl pyrazoles 2a—c. Method А.
A mixture of pyrazole 1а,b,c (1.5 mmol) and paraformaldehyde
(0.15 g) in CH2Cl2 (15 mL) was heated to reflux for 5 days. Unre-
acted paraformaldehyde was filtered off, and the filtrate was
concentrated.
Method B. Dried hydrogen chloride was bubbled through ab-
solute ethanol for 20 min. Pyrazole 1а—c (1.5 mmol) and para-
formaldehyde (0.15 g) were added, and the reaction mixture was
heated to reflux under argon for 4 h. Unreacted paraformaldehyde
was filtered off, and the filtrate was concentrated. Compounds
2а—с were recrystallized from 2 : 1 hexane—chloroform mixture.
1-(1-Hydroxymethyl)-5-methyl-4-[(4-methylphenyl)diazenyl]-3-
trifluoromethyl-1Н-pyrazole (2а). Yellow powder, 78% yield
(according to method A), 93% (according to method B), m.p.
146—147 C. IR, /cm–1: 3299 (ОН); 1605, 1583 (С=С, С=N);
1167—1143 (С—F). NMR 1Н,  2.43 (s, 3 Н, С6Н4—Me); 2.73
(s, 3 Н, 3-Me); 5.62 (s, 2 Н, СН2); 7.28—7.30 (m, 2 Н, Hm,
С6Н4); 7.75—7.77 (m, 2 Н, Ho, С6Н4). NMR 19F, : 99.93
(s, CF3). Found (%): С, 52.24; Н, 4.29; N, 18.67. С13Н13F3N4О.
Calculated (%): С, 52.35; Н, 4.39; N, 18.78.
The main crystallographic data for compound 3a and certain
experimental data are given in Table 1.
Synthesis of pyrazoles 1a—d (general procedure). Hydrazine
hydrate (1 mL, 12 mmol) and glacial acetic acid (10 mL) were
added to a solution of 1,3-diketone (10 mmol) in EtOH (20 mL),
and the resulting reaction mixture was heated under reflux for
8 h. On completion of the reaction water was added, the pre-
cipitate was filtered and recrystallized from 50% EtOH. Physico-
chemical characteristics of pyrazoles 1a,28 1b,31 and 1c32 are
consistent with the literature data.
1-(1-Hydroxymethyl)-5-phenyl-3-trifluoromethyl-1Н-pyr-
azole (2b). White powder, 74% yield (according to method A),
92% (according to method B), m.p. 94—96 C. IR, /cm–1: 3312
(ОН); 1603, 1587 (С=С, С=N); 1197—1132 (С—F). NMR 1Н,
 5.59 (s, 2 Н, СН2); 6.64 (s, 1 Н, Н(4)); 7.50—7.63 (m, 5 Н, Ph).
NMR 19F, : 99.53 (s, CF3). Found (%): С, 54.43; Н, 3.72; N, 11.43.
3-Heptafluoropropyl-4-[(4-methoxyphenyl)diazenyl]-5-meth-
yl-1Н-pyrazole (1d). Dark-orange powder, 78% yield, m.p.
142—144 C. IR, /cm–1: 3170 (NН); 1610, 1582 (C=C, C=N);
С
11Н9F3N2О. Calculated (%): С, 54.55; Н, 3.75; N, 11.57.

524
Russ. Chem. Bull., Int. Ed., Vol. 67, No. 3, March, 2018
Ivanova et al.
1-(1-Hydroxymethyl)-5-phenyl-3-(1,1,2,2-tetrafluoroethyl)-
References
-1Н-pyrazole (2с). White powder, 63% yield (according to
method A), 90% (according to method B), m.p. 96—98 C. IR,
/cm–1: 3305 (ОН); 1607, 1581 (С=С, С=N); 1205—1145
(С—F). NMR 1Н,  4.27 (t, 1 Н, ОН, J = 7.4 Hz); 5.58 (d, 2 Н,
СН2, J = 6.9 Hz); 6.11 (tt, 1 Н, Н(СF2)2, J = 53.5 Hz, J = 3.6 Hz);
6.65 (s, 1 Н, Н(4)); 7.49—7.63 (m, 5 Н, Ph). NMR 19F, : 26.04
(dt, 2 F, НCF2, J = 53.5 Hz, J = 6.3 Hz); 48.6 (td, 2 F, CF2,
J = 6.3 Hz, J = 3.9 Hz). Found (%): С, 52.11; Н, 3.63; N, 10.01.
С12Н10F4N2О. Calculated (%): С, 52.56; Н, 3.68; N, 10.22.
Synthesis of 1-alkoxymethyl pyrazoles 3a,d, 4a, and 5a.
A mixture of pyrazole 1a,d (0.45 mmol), paraformaldeldehyde
(0.35 g) in a corresponding alcohol (10 mL) with 0.3 mL of
concentrated HCl was heated at 80—90 C for 2—5 days
(monitoring by TLC). The reaction mixture was evaporated,
products 3a,d, 4a, and 5a were isolated by column chromato-
graphy, eluent: chloroform—ehtylacetate, 10 : 1.
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1-Ethoxymethyl-3-trifluoromethyl-5-methyl-4-[(4-methyl-
phenyl)diazenyl]-1Н-pyrazole (3a). Yellow powder, 30% yield,
m.p. 79—81 C. IR, /cm–1: 1610, 1583 (С=С, С=N); 1187—1142
1
(С—F). NMR Н,  1.19 (t, 3 Н, ОСН2Me, J = 7.0 Hz); 2.42
(s, 3 Н, С6Н4—Me); 2.70 (s, 3 Н, 3-Me); 3.59 (q, 2 Н, ОСН2Me,
J = 7.0 Hz); 5.52 (br. s, 2 Н, СН2); 7.28—7.30 (m, 2 Н, Hm, С6Н4);
7.75—7.76 (m, 2 Н, Ho, С6Н4). NMR 19F, : 100.0 (s, CF3).
Found (%): С, 55.13; Н, 5.21; N, 17.11. С15Н17F3N4О. Calculat-
ed (%): С, 55.21; Н, 5.25; N, 17.17.
1-Ethoxymethyl-3-heptafluoropropyl-5-methyl-4-[(4-meth-
oxyphenyl)diazenyl]-1Н-pyrazole (3d). Orange oil, 42% yield. IR,
/cm–1: 1603, 1585 (С=С, С=N); 1257—1209 (С—F). NMR
1Н,  1.17 (t, 3 Н, ОСН2Me, J = 7.0 Hz); 2.67 (s, 3 Н, 3-Me);
3.56 (q, 2 Н, ОСН2Me, J = 7.0 Hz); 3.88 (s, 3 Н, OMe); 5.55
(s, 2 Н, СН2); 6.98—7.00 (m, 2 Н, Hm, С6Н4); 7.81—7.83
(m, 2 Н, Ho, С6Н4). NMR 19F, : 35.64 (m, 2 F, -CF2); 52.23
(m, 2 F, -CF2); 81.7 (t, 3 F, CF3, J = 9.3 Hz). Found (%):
С, 46.37; Н, 3.81; N, 12.42. С17Н17F7N4О2. Calculated (%):
С, 46.16; Н, 3.87; N, 12.67.
1-Butoxymethyl-5-methyl-4-[(4-methylphenyl)diazenyl]-3-
trifluoromethyl-1Н-pyrazole (4a). Crystallizing orange oil, 57%
yield. IR, /cm–1: 1609, 1587 (С=С , С=N); 1237—1172 (С—F).
NMR 1Н,  0.88 (t, 3 Н, О(СН2)3Me, J = 7.4 Hz); 1.33 (m, 2 Н,
ОСН2СН2СН2Me); 1.53 (m, 2 Н, ОСН2СН2СН2Me); 2.43
(s, 3 Н, C6H4—Me); 2.70 (s, 3 Н, 3-Me); 3.52 (t, 2 Н,
ОСН2(CH2)2Me, J = 6.5 Hz); 5.53 (s, 2 Н, СН2); 7.29
(d, 2 Н, Hm, С6Н4, J = 8.2 Hz); 7.76 (d, 2 Н, Ho, С6Н4,
J = 8.2 Hz). NMR 19F, : 100.0 (s, CF3). Found (%): С, 57.82;
Н, 6.10; N, 16.00. С17Н21F3N4О. Calculated (%): С, 57.62; Н, 5.97;
N, 15.81.
1-Hexyloxymethyl-5-methyl-4-[(4-methylphenyl)diazenyl]-
3-trifluoromethyl-1Н-pyrazole (5a). Orange oil, 65% yield. IR,
/cm–1: 1608, 1582 (С=С, С=N); 1227—1162 (С—F). NMR
1Н,  0.89 (t, 3 Н, О(СН2)5Me, J = 6.8 Hz); 1.34 (m, 6 Н,
ОСН2СН2(СН2)3Me); 1.58 (m, 2 Н, ОСН2СН2(СН2)3Me);
2.43 (s, 3 Н, C6H4—Me); 2.70 (s, 3 Н, 3-Me); 3.52 (t, 2 Н,
ОСН2(CH2)4Me, J = 6.6 Hz); 5.52 (s, 2 Н, СН2); 7.28
(d, 2 Н, Hm, С6Н4, J = 8.3 Hz); 7.76 (d, 2 Н, Ho, С6Н4,
J = 8.3 Hz). NMR 19F, : 100.0 (s, CF3). Found (%): С, 59.63;
Н, 6.47; N, 14.72. С19Н25F3N4О. Calculated (%): С, 59.67;
Н, 6.59; N, 14.65.
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The present work was financially supported by the
Russian Science Foundation (Project No. 16-13-10255).
Received November 21, 2017;
accepted January 16, 2018