Three-Component Reaction of Sulfonamides with Acetylene and Amines

Article abstract of DOI:10.1134/S107042801902009X

N-(2-Phenyl-1-piperidin-1-ylethylidene)tosylamide was synthesized by oxidative coupling of arenesulfonamides, acetylenes, and secondary amines. The reaction of phenylacetylene or propargyl alcohol with triflamide and piperidine under the same conditions u

Full text of DOI:10.1134/S107042801902009X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 2, pp. 179–185. © Pleiades Publishing, Ltd., 2019.
Russian Text © B.A. Shainyan, V.I. Meshcheryakov, I.V. Sterkhova, 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 2, pp. 227–233.
Three-Component Reaction of Sulfonamides with Acetylene
and Amines
a,
a
a
B. A. Shainyan *, V. I. Meshcheryakov , and I. V. Sterkhova
a
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*
е-mail: bagrat@irioch.irk.ru
Received November 7, 2018; revised November 21, 2018; accepted December 17, 2018
Abstract—N-(2-Phenyl-1-piperidin-1-ylethylidene)tosylamide was synthesized by oxidative coupling of
arenesulfonamides, acetylenes, and secondary amines. The reaction of phenylacetylene or propargyl alcohol
with triflamide and piperidine under the same conditions unexpectedly gave N-[(1E)-piperidin-1-
5
ylmethylidene]triflamide TfN=CHNC H10 as a result of cleavage of the triple bond in the alkyne. A similar
reaction with benzoylacetylene gave (2Е)-1-phenyl-3-piperidin-1-ylprop-2-en-1-one, while triflamide did not
react. Adducts of a series of acetylenes with triflamide were obtained using triflamide sodium salt. Attempted
synthesis of an N-triflyl-substituted analog of amidine 1 by the reaction of benzoylacetylene with triflamide and
piperidine or morpholine in the presence of Cu(OTf)
2
and hydrogen peroxide as an oxidant unexpectedly gave
1
-piperidin-1-yl- or 1-morpholin-1-ylmethanimine, respectively.
Keywords: amidines, sulfonamides, acetylenes, amines, oxidative coupling, XRD analysis
DOI: 10.1134/S107042801902009X
Amidines containing an electron-acceptor group on
the imino nitrogen atom present interest in view of the
described by Kim and Stahl [8] for the reaction of
arylacetylenes with dialkylamines and arenesulfon-
strong conjugation in the >N–CH=N–Х triad. A amides (Scheme 1).
number of synthetic approaches to perfluoroalkylsul-
The reaction by Scheme 1 resulted in the successful
fonylamidines R SO N=CHNR are known, including
f
2
2
synthesis of N-[2-phenyl-1-(piperidin-1-yl)ethylede-
ne)-4-methylbenzenesulfonamide 1. The structure of
compound 1 was established by X-ray diffraction
XRD) analysis (Fig. 1). Selected structural parameters
of the synthesized compound are listed in the table.
the reaction of R SO F with DMF [1], Vilsmeier−Haack
f
2
reaction of salts R SO NHNa with POCl and R NCHO
F
2
3
2
[
2], three-component reaction of azides R SO N with
f 2 3
(
ketones and secondary amines [3, 4], and some other
5]. We previously synthesized the simplest amidine of
this type, TfN=CH–NMe (Tf = CF SO ), by the
[
The independent part of the unit cell of amidine 1
contains one molecule. Molecules 1 are held together
2
3
2
reaction of 2-phenyl-2H-1,2,3-triazole-4-carboxylic
acid chloride with TfNHNa in DMF [6], and recently
developed a method of synthesis of N-triflylamidines
from N-formylamines and N-sulfinyltriflamide [7].
Proceeding with this research we made an attempt to
2
6
by short S–O···H–C contacts of 2.5–2.7 Å. The N –C
6
1
and C =N bonds in molecule 1 have almost equal
lengths, which suggests strong conjugation, even though
it is not as strong as in its С-unsubstituted triflyl
bring triflamide into a Cu(OTf) -catalyzed three-
analog TfN=CH–N(CH ) [7]. Note that the N–C and
2 5
2
component oxidative coupling reaction with terminal
C=N bond lengths in the structurally related molecule
acetylenes and secondary аmines under the conditions
TsN=CH–NEt
2
are equal to each other (1.307 Å) [9].
Scheme 1.
NR R2
1
Cu(OTf) , O
2
2
R
1
2
3
R
C
CH
R R NH
+
R SO NH
2 2
+
o
Toluene, 70 C, 15 h
NSO R3
2
1
79

1
80
SHAINYAN et al.
The unusual nature of this reaction is that it
2
C
3
formally involves the cleavage of the triple bond, so
that the final product contains only one carbon atom
from the parent acetylene. Obviously, this can only
occur as the result of addition to the triple bond, i.e. its
saturation to an ordinary bond, and subsequent
cleavage of the latter. An example of such a cleavage
in the reaction of ketones with arylacetylenes and
guanidine was recently reported by Schmidt et al. [10].
C
1
C
4
C
5
1
7
C
2
C
O
1
8
1
9
C
C
2
0
C
6
14
1
7
C
C
S
C
2
10
N
C
1
3
C
1
12
N
11
C
1
8
C
The driving force of the elimination of fragments of
the starting arylacetylene in [10] is aromatization of
the intermediate cycloadduct to 2-аminоpyrimidine. In
our case, such a driving force, apparently, is the
oxidation of the intermediate adduct with sodium
periodate (Scheme 3).
C
1
6
O
C
9
C
15
C
Fig. 1. Molecular structure of compound 1.
Under the conditions of the reaction in Scheme 1,
With benzoylacetylene, the single product of the
three-component reaction with piperidine and
triflamide is compound 3 (Scheme 4) formed as the
trans-isomer through the addition of the amine, which
is more basic than triflamide, to the activated triple
bond. The NMR spectra of the product coincide with
the spectra of (2Е)-1-phenyl-3-piperidin-1-ylprop-2-
en-1-one prepared in different ways [11–15].
phenylacetylene did not react with triflamide and
piperidine or diisopropylamine as an аmine
component. However, by changing the reaction
conditions, specifically, by replacing the Cu(OTf)2
catalyst by CuI, the О oxidant by NaIO , and the
2
4
solvent by acetonitrile, we unexpectedly obtained N-
(piperidin-1-yl)methylidene)triflamide 2, which we
[
synthesized earlier [7]. The reaction result is
independent on the substituent at the triple bond, as
judged from the fact that amine 2 is also formed, when
phenylacetylene is replaced by propargyl alcohol
Attempted addition of triflamide to benzoyl-
acetylene under the same conditions but in the absence
of аminа failed because of the extremely low basicity
of triflamide. The adduct of triflamide to
(
Scheme 2).
Some bond lengths, valence and torsion angles in a molecule 1.
Bond
l, Å
Angle
φ, deg
Angle
θ, deg
1
1
1
1
2
1
1
1
1
1
6
6
S –O
1.4434(11)
1.4475(12)
1.6069(13)
1.7670(15)
1.3282(18)
1.3341(19)
1.4730(19)
1.4758(19)
1.520(2)
O –S –O
115.92(7)
105.48(7)
115.08(7)
107.84(7)
108.00(7)
103.65(7)
125.37(11)
125.02(13)
122.55(12)
112.27(12)
116.87(13)
125.43(13)
117.64(12)
O –S –N –C
–169.50(12)
–40.41(14)
77.28(13)
–167.22(11)
15.6(2)
1
2
1
1
1
2
1
1
S –O
O –S –N
O –S –N –C
1
2
1
7
1
1
6
S –N
O –S –N
C –S –N –C
1
7
1
1
7
7
7
1
1
1
6
2
S –C
O –S –C
S –N –C –N
1
6
2
1
1
1
6
5
N –C
O –S –C
S –N –C –C
2
6
1
1
12
2
6
1
N –C
N –S –C
C –N –C –N
–178.12(13)
–3.18(19)
–0.7(2)
2
12
16
6
6
1
16
2
6
1
N –C
C –N –S
C –N –C –N
2
6
2
12
16
12
2
6
5
N –C
C –N –C
C –N –C –C
5
6
2
16
2
6
5
C –C
C –N –C
C –N –C –C
174.25(12)
106.49(16)
–70.70(16)
83.45(13)
–92.15(13)
1
2
2
16
4
5
6
1
C –N –C
C –C –C –N
1
6
2
4
5
6
2
N –C –N
C –C –C –N
1
6
5
1
1
7
8
N –C –C
N –S –C –C
2
6
5
1
1
7
19
N –C –C
N –S –C –C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

THREE-COMPONENT REACTION OF SULFONAMIDES WITH ACETYLENE AND AMINES
181
Scheme 2.
R = Ph, CH OH
2
CuI, NaIO4
TfN=CH
N
MeCN
R
C
CH
+
NH
+
TfNH2
2
R = Ph, Cu(OTf)2
Toluene, O2,
7
0oC, 15 h
Scheme 3.
TfNH2
[O]
R
C
CH
+
NH
R
CH CH
N
RCH2 CH
NHTf
N
2
+
RCHO
_
H O
2
benzoylacetylene could only be obtained, when the
basicity of triflamide was increased by using its
sodium salt TfNHNa, and the reaction was performed
spectrum contains, along with signals of Z,E-4, a
doublet at 3.3 ppm and a triplet at 4.9 ppm (ratio 2 : 1),
split by mutual coupling with a constant of 5.6 Hz
in the presence of Cu(OTf) as a catalyst and in the
characteristic of the –CH CH=N– fragment and
2
2
absence of oxidant. Similar reactions of TfNHNa with
other activated acetylenes, specifically dibenzoyl-
acetylene, methyl acetylenecarboxylate, and dimethyl
acetylenedicarboxylate gave adducts 5–7 (Scheme 5).
belonging to the methylene and azomethine protons of
1
3
this fragment. The С NMR spectrum displays the
methylene and carbonyl carbon signals at 53.3 and
196.9 ppm, respectively. The carbonyl carbon signal of
compound 8 is downfield to the respective signal of
isomer 4, as would be expected for an unconjugated
С=О group. Presumably, the formation of imine 8 is
promoted by the involvement of methanol into a
solvation complex and keto-enol isomerization of the
latter (Scheme 6).
1
13
According to the Н and С NMR data, adducts 4–
7
are formed as mixtures of two isomers in comparable
proportions, but, depending on the substituents, either
Z or E isomer is prevailing: Z-4 : E-4 = 3 : 10, Z-5 :
E-5 = 2.2 : 1, Z-6 : E-6 = 1 : 3, and Z-7 : E-7= 1 : 1.8.
Isomer E-4 was isolated pure by column
chromatography on silica gel, and this allowed us to
Attempted synthesis of an N-triflyl-substituted
1
3
assign the signals in its С NMR spectrum.
analog of amidine
benzoylacetylene with triflamide and piperidine in the
presence of 5 mol % of Cu(OTf) in dioxane and
1
by the reaction of
As follows from Scheme 5, products 4–7 are
formed as the enamine tautomers. However, according
2
1
13
to the Н and С NMR data, the reaction with
benzoylacetylene in methanol gave, along with Z-4 and
hydrogen peroxide as an oxidant unexpectedly gave 1-
(piperidin-1-ylmethanimine 9. Similarly, the reaction
with morpholine in acetonitrile or ethyl methyl ketone
resulted in the synthesis of 1-(morpholin-1-yl)me-
thanimine 10. Seemingly, there results are reasonably
E-4, the imine tautomer PhC(O)CH CH=NTf (8), and
2
the Z,E-4 : 8 ratio was 0.7 : 1. The formation of
1
compound 8 is confirmed by the fact that the Н NMR
Scheme 4.
CuI, NaIO4
MeCN
PhCOC
CH
+
NH
+
TfNH
2
PhCOCH=CH
N
3
Scheme 5.
R
NHTf
R
R'
Cu(OTf)2
MeCN
RC
CHR'
TfNHNa
+
C
C
+
C
C
H
R'
H
NHTf
4_
7 Z
4_7 E
R = PhC(O), R' = H (4); R = R' = PhC(O) (5); R = MeOC(O), R' = H (6); R = R' = MeOC(O) (7).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

1
82
SHAINYAN et al.
Scheme 6.
CH
CH
CH
CH
PhC
NTf
PhC
NTf
4
-Z
8
OH
H
O
H
H
O
O
Me
Me
Scheme 7.
Cu(OTf)2
PhCOC
CH
+
X
NH
+
TfNH2
X
N
H O , 30%
2
2
NH
9
1
(X = CH2)
0 (X = O)
PhCOCH2 CH
NHTf
N
A
_TfOH
H O
2
2
[
O]
PhCOOH
PhCOCH OH
+
X
N
CH
OH
2
_CO2
NHTf
B
explained in terms of the oxidation of intermediate А,
like that in Scheme 3, with С–С bond cleavage and
formation of benzoic acid and N-[аminо(hydroxy)-
methyl]triflamide B, followed by TfOH elimination
from the latter (Scheme 7).
using SHELX [16]. Absorption was included using
SADABS. Non-hydrogen atoms were refined with
anisotropic displacement parameters using SHELX
[16]. The crystal data are deposited at the Cambridge
Crystallographic Data Center (www.ccdc.cam.ac.uk/
data_request/cif), CCDC 1826686.
Evidence for Scheme 7 is provided by the isolation
of benzoic acid by preparative chromatography and its
N-[2-Phenyl-1-(piperidin-1-yl)ethylidene]-4-me-
thylbenzenesulfonamide (1). A solution of 1.03 g
(6 mmol) of tosylamide in 20 mL of dry toluene
1
and identification of Н NMR spectroscopy. The
structure of products 9 and 10 was confirmed by IR
and NMR spectroscopy.
containing 0.05 g (0.15 mmol) of Cu(OTf) was
2
evacuated 3 times and purged with oxygen, after which
0.31 g (3 mmol) of phenylacetylene, 0.51 g (6 mmol)
of piperidine, and 10 mL of toluene were added. A
stream of oxygen was passed through the mixture for
15 h under vigorous stirring and heating at 70°С. After
cooling, a precipitate formed and was dissolved in
10 mL of ethyl acetate, the solution was filtered
through a bed of silica gel, the solvent was removed in
a vacuum, and the residue was chromatographed on an
EXPERIMENTAL
The IR spectra were measured on a Varian 3100
1
13
19
FTIR spectrometer. The H, C, and F NMR spectra
were run on a Bruker DPX 400 spectrometer at 400
1
13
19
(
Н), 100 ( С), and 376 ( F) МHz in DMSO-d . The
6
1
13
H and C chemical shifts were measured against
residual proton signals of the deuterated solvent and
given in ppm relative to TMS, and those of F, relative
19
1
alumina column with hexane–ethyl acetate, 1 : 1. H
to CFCl . The single crystal of compound 1 was
NMR spectrum, δ, ppm: 1.08 m (2Н, NCH CH CH ),
3
2
2
2
obtained by crystallization of the eluate (ethyl acetate–
hexane) after column chromatography. Reaction
progress was monitored by TLC on Sorbfil plates.
XRD analysis was performed on a Bruker D8 Venture
1.45 m (4Н, NCH CH ), 3.33 and 3.65 m (4H, NCH ),
2 2 2
3
,5
4.39 s (2H, PhCH ), 7.18–7.34 m (7H, Ph and H in
2
2
,6
13
Tol) 7.68 d (2H, H in Tol, J 8.1 Hz). C NMR spec-
trum, δ, ppm: 20.8 (СН ), 23.2 (NCH CH CH ), 24.9 and
3
2
2
2
diffractometer (MoK radiation, λ 0.71073 Å, φ and ω
scans). The structure was solved by the direct method
25.4 (NCH CH ), 35.8 (PhCH ), 45.3 and 47.3 (NCH ),
125.7 (C in Tol), 126.5 (C in Ph), 128.0 (C in Ph),
α
2 2 2 2
2
,6
p
m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

THREE-COMPONENT REACTION OF SULFONAMIDES WITH ACETYLENE AND AMINES
183
3
,5
o
1
1
1
28.5 (C in Tol), 129.2 (C in Ph), 134.9 (C in Ph),
purified by column chromatography on silica gel,
eluent hexane–ether–acetonitrile, 1 : 2 : 1, to obtain
4
1
41.47 (C in Tol), 141.54 (C in Tol), 164.0 (C=N). Found,
%
: С, 67.85; Н, 6.45; N, 7.85; S, 8.98 C H N O S.
yellow crystals, mp 89–91°С (91–92°С [11], 90–91.5°С
2
0
24
2
2
1
Calculated, %: С, 67.38; Н, 6.79; N, 7.86; S, 8.99.
[12]). H NMR spectrum, δ, ppm: 1.57 m (6H, 3CH
2
),
3
.41 m [4H, (CH ) N], 5.98 d (1H, J 12.4 Hz), 7.65 d
2 2
XRD analysis of compound 1: C H N O S, m
56.48, colorless plate-like crystals, 0.08 × 0.20 ×
2
0
24
2
2
m+p
(
1H, J 12.4 Hz), 7.40–7.49 m (3H, Н ) 7.88 m (2H,
3
0
2
о
13
Н ). C NMR spectrum, δ, ppm: 24.6, 25.4 br, 45.8 br,
5
.30 mm, monoclinic, space group P2 /c; θ /θ
1
min max
4.0 br, 90.1, 127.1, 128.0, 130.6, 140.3, 152.7, 186.0.
.67/30.25; T 100 K, a 19.522(1), b 8.325(1), c
3
1
1.354(1) Å; β 97.906(2)°, V 1827.8(2) Å , Z 4, d
Compound 3 was also prepared by the reaction of
calc
3
1
0
2
0
–
1
.295 g/cm , F(000) 760; absorption coefficient μ
.193 mm ; 77175 reflections, including 5412 unique;
0.87 g (6.7 mmol) of benzoylacetylene and 0.13 g
(0.67 mmol) of CuI in 20 mL of dry acetonitrile with a
solution of 0.85 g (10 mmol) of piperidine in 5 mL of
dry acetonitrile with a raw yield of 1.59 g (92 %).
–
1
27 refined parameters; R 4.40, R (on all reflections)
w
2
.068; goodness of fit on F 1.054; Δρmax/Δρmin 0.350/
3
2
2
0
2
0.396 e/Å ; weight scheme w = [σ (F ) + (0.0392P) +
N-(3-Oxo-3-phenylprop-1-en-1-yl)trifluorome-
thanesulfonamide (4). To a solution of 1 g (7.7 mmol)
of benzoylacetylene in 20 mL of dry acetonitrile we
–
1
2
2
.3952P] , where P = (F + 2Fc )/3.
0
N-(Piperidin-1-ylmethylidene)trifluoromethane-
sulfonamide (2). To a solution of 1.0 g (6.7 mmol) of
triflamide in 15 mL of dry acetonitrile, cooled to 10°С
we added 0.13 g (0.67 mmol) of CuI and 0.34 g
added 0.14 g (0.39 mmol) of Cu(OTf) and 1.97 g
2
(11.5 mmol) of triflamide sodium salt. The mixture
was stirred at 40–45°С for 4–5 h, cooled, the
precipitate was filtered off, and the solvent was
removed at reduced pressure. According to the NMR
data, the yellow green residue contained a mixture of
the Z and E isomers of compound 4. IR spectrum, KBr,
(
3.4 mmol) of phenylacetylene and then slowly,
dropwise, a solution 0.57 g (6.7 mmol) of 5 mL of dry;
therewith, the mixture slightly warmed up and
acquired a blue-green color. After cooling to room
–
1
temperature, 2.15 g (10 mmol) of NaIO was added in
ν, cm : 3444 (NH), 3063 (CH), 1641 (C=O), 1584
4
1
small portions. The mixture was allowed to stand for
(C=C), 1557 (arom), 1197, 1177 (CF). Isomer (Z)-4: H
3
0 min and heated to 40°С, after which it
NMR spectrum, δ, ppm: 5.77 d (1Н, СОСН=, J 8.1 Hz),
7.15 d (1Н, =СНNTf, J 8.1 Hz). The aromatic proton
spontaneously warmed up to ~50°С and became
brown. The mixture was stirred for 1 h at 50°С and
then 3 h at room temperature, monitoring the reaction
progress by TLC. The reaction mixture was filtered,
the solvent was removed at reduced pressure, and the
residue was purified by column chromatography on
silica gel, eluent hexane–ether–acetonitrile, 1 : 2 : 1, to
obtain colorless plate-like crystals, mp 88–89°С,
identical to those obtained in [7].
13
signals of the two isomers overlap. C NMR
o
spectrum, δ, ppm: 100.8 (СОСН=), 127.4 (С ), 128.1
m
p
ipso
(С ), 130.9 (С ), 140.6 (С ), 152.6 (=СHN), 187.1
1
9
(С=О). F NMR spectrum, δ, ppm: –78.72. The (E)-4
isomer was isolated by column chromatography on
silica gel (eluent hexane–ether–acetonitrile, 1 : 2 : 1) as
a broght yellow solid amorphous material, yield 65%.
H NMR spectrum, δ, ppm: 6.27 d (1Н, СОСН=, J 12.5
Hz), 7.44 t (2Н, Н , J 7.6 Hz), 7.50 t (1Н, Н , J 7.3
Hz), 7.83 d (2Н, Н , J 7.7 Hz), 8.02 d (1Н, =СНNTf, J
2.5 Hz).
СОСН=), 120.6 q (CF , J 323.9 Hz), 127.3 (С ),
28.2 (С ), 131.1 (С ), 139.8 (С ), 157.7 (=СHN),
1
m
p
1
-Phenyl-3-piperidin-1-ylprop-2-en-1-one (3). To
о
a solution of 1.49 g (10 mmol) of triflamide in 20 mL
of dry acetonitrile we added 0.13 g (0.67 mmol) of CuI
and 0.87 g (6.7 mmol) of benzoylacetylene (the
mixture acquired a bright orange color) and then
slowly, dropwise, a solution of 0.85 g (10 mmol) of
piperidine in 5 mL of dry acetonitrile (the mixture
slightly warmed up and acquired a brown green color).
After cooling to room temperature, 2.9 g (13.4 mmol)
13
1
C NMR spectrum, δ, ppm: 100.8
о
(
1
1
3
m
p
ipso
1
9
89.0 (С=О). F NMR spectrum, δ, ppm: –79.06.
HRMS, m/z: 280.0298 [M + H] . Calculated for
+
C H F NO S: 280.0255.
1
0
9
3
3
The reactions of TfNHNa with dibenzoylacetylene,
of NaIO was added in small portions. The mixture
methyl acetylenecarboxylate, and dimethyl acetylene-
dicarboxylate were performed in a similar way. The
residue after removal of the solvent was analyzed by
Н, С, and F NMR spectroscopy, not isolating
analytically pure samples.
4
was allowed to stand for 30 min, heated to ~50°С, and
stirred for 3 h, monitoring the reaction progress by
TLC. The reaction mixture was filtered, the solvent
was removed at reduced pressure, and the residue was
1
13
19
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

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84
SHAINYAN et al.
N-[3-Oxo-3-phenyl-1-(phenylcarbonyl)prop-1-en-
(СН=), 120.9 q (CF , J 326.6 Hz), 149.2 (=СHN),
165.7 (С =О), 167.8 (С =О). F NMR spectrum, δ,
ppm: –77.74.
3
2
3
19
1
-yl]trifluoromethanesulfonamide Z,E-5. IR
–
1
spectrum, KBr, ν, cm : 3390, 3278 (NH), 3065, 2927
CH), 1700, 1659 (C=O), 1621, (C=C), 1597, 1576,
508 (arom), 1223, 1191, 1176, 1120 (CF). Z-5 (major
(
1
1
-(Piperidin-1-yl)methanimine (9). To a solution of
.65 g (5 mmol) of benzoylacetylene, 0.97 g (6.5 mmol)
of triflamide, and 0.09 g (0.25 mmol) of Cu(OTf) in
0
1
isomer). H NMR spectrum, δ, ppm: 6.95 s (1Н, СН=),
m+p
о
2
7
7
.38–7.64 m (6Н, Ph ), 7.74 d (2Н, 4-Ph , J 7.4 Hz),
1
5 mL of dioxane we slowly added dropwise a solution
о
13
.85 d (2Н, 1-Ph , J 7.4 Hz). C NMR spectrum, δ,
of 0.64 g (7.5 mmol) of piperidine in 5 mL of dioxane.
The mixture was allowed to stand for 30 min at room
temperature and then for 2 h at 60°С; therewith, the
mixture changed color from green to dark yellow.
After cooling to 10°С, 3 mL of 30% Н О was slowly
ppm: 101.1 (СН=), 121.0 q (CF , J 327.4 Hz), 127.2
3
o
о
m
(
1
С in 4-Ph), 128.2 (С in 1-Ph), 128.4 (С in 4-Ph),
28.6 (С in 1-Ph), 131.8 (С in 4-Ph), 132.4 (С in 1-
Ph), 135.3 (С in 4-Ph), 138.8 (С in 1-Ph), 164.2
=СHN), 186.7 (С =О), 193.9 (С =О). F NMR
spectrum, δ, ppm: –76.39. E-5 (minor isomer). H
NMR spectrum, δ, ppm: 5.75 s (1Н, СН=), 7.38–7.64
m (6Н, Ph ), 7.80 d (2Н, 4-Ph , J 7.5 Hz), 7.92 d
m
p
p
ipso
ipso
4
1
19
2
2
(
added dropwise, and the mixture was stirred for 2 h at
room temperature and filtered. The solvent was
removed in a vacuum to leave a light yellow material.
Part of the residue was distilled (bp 90–96°С/3 mmHg).
However, the mixture could not be separated in this
way, and therefore, compound 9 was isolated
by preparative chromatography on an Agilent
1
m+p
о
о
13
(
1
-
2Н, 1-Ph , J 7.5 Hz). C NMR spectrum, δ, ppm:
о
04.0 (СН=), 120.5 q (CF , J 325.5 Hz), 127.6 (С in 4
3
о
m
m
Ph), 129.3 (С in 1-Ph), 128.3 (С in 4-Ph), 128.4 (С
p
p
in 1-Ph), 131.5 (С in 4-Ph), 132.9 (С in 1-Ph), 136.0
in 1-Ph), 157.9 (=СHN),
88.1 (С =О), 196.2 (С =О). F NMR spectrum, δ,
1
200 Preparative HPLC System. IR spectrum
ipso
ipso
(С
in 4-Ph), 140.0 (С
–1
1
(CH Cl ), ν, cm : 3414 (NH), 1657 (C=N). H NMR
4
1
19
2 2
1
spectrum (CD CN), δ, ppm: 1.48 m (2Н, 4-CH ), 1.55
3
2
ppm: –77.51.
and 1.66 m (4Н, 3,5-CH ), 3.31 and 3.40 m (4H,
2
1
3
Methyl 3-(trifluoromethanesulfonamido)prop-2-
NCH
2
), 6.84 br.s (1H, NH), 7.93 s (1H, CH=N).
C
–
1
enoate Z,E-6. IR spectrum (ATR), ν, cm : 3329 (NH),
959 (CH), 1678 (C=O), 1605 (C=C), 1172, 1146 1120
NMR spectrum (CD CN), δ, ppm: 25.4 (СН ), 26.0
3
2
2
(
(CH ), 27.3 (CH ), 41.1 (CH ), 47.4 (CH ), 161.9
2
2
2
2
1
CF). Z-6 (minor isomer). H NMR spectrum, δ, ppm:
(C=N).
3
6
.50 s (3Н, ОСН ), 4.58 d [1Н, =СНС(О), J 8.3 Hz],
.94 d (1Н, =СНN, J 8.3 Hz). C NMR spectrum, δ,
3
1
-(Morpholin-1-yl)methanimine (10) was
1
3
prepared in a similar way in acetonitrile or ethyl
methyl ketone and isolated by column chromatography
on silica gel. H NMR spectrum (CD CN), δ, ppm:
.36 m (2Н, NCH ), 3.45 m (2Н, NCH ), 3.57 m (2Н,
OCH ), 3.62 m (2H, OCH ), 7.98 s (1H, CH=N). The
NH proton signal was not observed in the H NMR
spectrum in acetonitrile, probably, because of fast
ppm: 49.7 (ОСН ), 94.1 [=СНС(О)], 120.9 q (CF , J
3
spectrum, δ, ppm: –77.20. E-6 (major isomer). H
NMR spectrum, δ, ppm: 3.51 s (3Н, ОСН ), 4.96 d
3
3
1
9
27.0 Hz), 151.8 (=СHN), 166.5 (С=О). F NMR
1
1
3
3
2 2
3
2
2
[1Н, =СНС(О), J 13.0 Hz], 7.75 d (1Н, =СНN, J
1
1
3
1
9
3.0 Hz). C NMR spectrum, δ, ppm: 50.0 (ОСН3),
6.7 [=СНС(О)], 120.9 q (CF , J 327.0 Hz), 155.4
13
3
exchange with the solvent. C NMR spectrum
2
19
(
=СHN), 167.14 (С =О), 169.1 (С=О). F NMR
(
(
CD CN), δ, ppm: 41.1 (NСН ), 46.5 (NCH ), 67.0
3 2 2
spectrum, δ, ppm: –77.51.
ОCH ), 67.9 (ОCH ), 162.1 (C=N).
2
2
Dimethyl 2-(trifluoromethanesulfonamido)but-2-
–
1
enedioate Z,E-7. IR spectrum (film), ν, cm : 3313
(
(
FUNDING
The work was financially supported by the Russian
NH), 2959, 2922, 2855 (CH), 1712 (C=O), 1599
1
C=C), 1188, 1120 (CF). Z-7 (minor isomer). H NMR
spectrum, δ, ppm: 3.49 s (3Н, ОСН ), 5.33 s (1Н,
Foundation for Basic Research (project no. 17-03-
00213-а) and performed using the equipment of the
Baikal Center for Collective Use, Siberian Branch,
Russian Academy of Sciences.
3
1
3
СН=).
C NMR spectrum, δ, ppm: 50.24 (3-
СООСН ), 51.5 (2-СООСН ), 94.7 (СН=), 121.0 q
3
3
2
(
1
7
CF , J 327.8 Hz), 155.9 (=СHN), 167.14 (С =О),
67.18 (С =О). F NMR spectrum, δ, ppm: –76.55. E-
(major isomer). H NMR spectrum, δ, ppm: 3.53 s
3Н, ОСН ), 5.31 s (1Н, СН=). C NMR spectrum, δ,
3
3
19
1
CONFLICT OF INTEREST
1
3
(
3
ppm: 50.17 (3-СООСН ), 51.9 (2-СООСН ), 103.2
The authors declare no conflict of interest.
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019

THREE-COMPONENT REACTION OF SULFONAMIDES WITH ACETYLENE AND AMINES
185
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 2 2019