Arylmethylene-3H-furan(pyrrol)-2-ones in reactions of [3+2]-cycloaddition with activated hydrazones

Article abstract of DOI:10.1134/S1070428014050078

Spiropyrrolidine derivatives were synthesized for the first time by [3+2]-cycloaddition of 3-arylmethylene-3H-furan(pyrrol)-2-ones to N-benzylidenebenzylamine activated by the system AcOAg-Et₃N. The reaction route and the spectral characteristi

Full text of DOI:10.1134/S1070428014050078

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 5, pp. 659–661. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.E. Kamneva, A.Yu. Egorova, A.B. Trankovskii, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 5, pp. 673–
675.
Arylmethylene-3Н-furan(pyrrol)-2-ones in Reactions
of [3+2]-Cycloaddition with Activated Hydrazones
I. E. Kamneva, A. Yu. Egorova, and A. B. Trankovskii
Chernyshevskii Saratov State University, Astrakhanskaya ul. 83, Saratov, 410012 Russia
e-mail: kwirina1982@mail.ru
Received June 18, 2013
Abstract—Spiropyrrolidine derivatives were synthesized for the first time by [3+2]-cycloaddition of 3-
arylmethylene-3Н-furan(pyrrol)-2-ones to N-benzylidenebenzylamine activated by the system AcOAg–Et3N.
The reaction route and the spectral characteristics of the first obtained compounds have been discussed.
DOI: 10.1134/S1070428014050078
The development of preparation procedures for new
spiroheterocyclic structures, analogs of natural
alkaloids, is an important task of the modern organic
chemistry. One among the possible synthetic ways to
these compounds is the 1,3-dipolar cycloaddition
which permits building up various heterocyclic
systems in one stage under mild conditions [1–5]. The
range of applicability of this reaction is limited by the
presence in the dipolarophile molecule of a sufficiently
active double bond and by the absence of shielding
groups.
four π-electrons distributed among three atoms. Nitrile
oxides, nitrile ylides, carbonyl ylides, azomethine
imides, azomethine ylides, diazo compounds, etc may
serve as examples of these compounds.
Nitrile imine is a 1,3-dipole generated in situ by the
action of triethylamine and silver acetate on
diarylhydrazone and containing two nitrogen atoms
and one terminal sp2-hybridized carbon atom. 2-
Azaallyl ion stabilized with a silver cation provides a
high stereoselectivity of the 1,3-dipolar cycloaddition.
The reaction between the 3-arylmethylene-3Н-
furan(pyrrol)-2-one and diarylhydrazone was carried
out at equimolar reagents ratio in acetonitrile at room
temperature. Silver acetate and triethylamine was used
as the catalyst. Depending on the diarylhydrazone
structure diverse reaction products may be expected
(see Scheme 1).
The dipolarophiles that we have chosen, 3-
arylmethylene-3Н-furan-2-ones, contain in their
structure a conformationally localized s-cis-enone
fragment [6] providing a possibility to carry out the
1,3-dipolar cycloaddition with their participation.
Formerly compounds from the series of 3-
arylmethylene-3Н-furan-2-ones were subjected to the
following reactions at the double bond of the
heterocycle: reactions of Michael, Friedel–Krafts, and
bromination [7]. The reactions with nucleophilic
reagents and ethyl diazoacetate occurred with the
opening of the furan ring.
1
The presence in the Н NMR spectra of compounds
I–VIII of two singlets belonging to the protons attached
to the tertiary carbon atoms at 4.08–4.26 and 4.35–
4.54 ppm indicates unambiguously the formation of a
single isomer. The signal of the proton at the nitrogen
atom of the pyrazolidine fragment resonates in the region
8.32–8.47 ppm, the singlet of the proton at the nitrogen of
the pyrrolinone ring appears in the region 8.06–8.21 ppm.
The compounds applied as 1,3-dipoles should
possess a common structural feature: They should have
Scheme 1.
Ph
N
Ph
AcOAg
Ph
N
Ph
Ph
N
Ph
N
Ph
Ph
Ph
N
Ph
N
N
N
N
N
H
Ag+
659

KAMNEVA et al.
660
Scheme 2.
H
N
Ph
R2
Ph
N
X
R2
R1
O
N
Ph
N
Ph
+
N
H
N
Ph
R2
Ag+
Ph
R1
O
X
R1
O
X
I_ VIII
X = NH: R1 = 4-MeC6H4, R2 = 2-ClC6H4 (I); R1 = Ph, R2 = 2-ClC6H4 (II); R1 = 4-MeC6H4, R2 = Ph (III), 3,4-OCH3C6H4
(IV), 3-NO2C6H4 (V); R1 = Ph, R2 = 3-NO2C6H4 (VI); X = O: R1 = 4-MeC6H4, R2 = 2-OHC6H4 (VII); R1 = Ph, R2 = 2-
ClC6H4 (VIII).
The number, location, and the multiplicity of the signals
are in total agreement with the assumed structure.
and 13С NMR spectra were registered on a spectrometer
Bruker MSL-400, internal reference TMS, solvent
DMSO-d6. The homogeneity of compounds was checked
by TLC on Silufol plates, eluent ethyl acetate–hexane–
chloroform, 2 : 2 : 1, development in iodine vapor.
The 13С NMR spectra of compounds I–VIII
contain a signal from the tertiary carbon atom (68.83–
72.63 ppm), signals of aliphatic sp3-hybridized carbon
atoms of the pyrazolidine ring (57.8–65.63 ppm), a
series in the downfield region of the signals from sp2-
hybridized carbon atoms (119.81–167.39 ppm) among
which the signal from the carbonyl carbon should be
mentioned (165.92–167.39 ppm). The signal of the
carbon atom of the double bond from the pyrrolinone
ring appears in the region 95.46–102.76 ppm (Scheme 2).
5-R-3-Arylmethylene-3Н-furan(pyrrol)-2-ones
were obtained by the known procedure [8].
Compounds I–VIII. To a solution of 1.8 mmol of
N-benzylidenebenzylamine in 18 mL of acetonitrile
was added 1.8 mmol of 3-arylmethylidene-3Н-furan-
(pyrrol)-2-one, 1.8 mmol of triethylamine, and 15 mol %
of silver acetate. The reaction mixture was heated at
continuous stirring till the dissolution of the initial
reagents and afterwards it was left standing at room
temperature for 2–3 days. The precipitate of silver
acetate was filtered off, the reaction mixture was
neutralized with ammonium chloride solution, the
organic layer was separated and evaporated. The
crystals obtained were recrystallized from ethanol, 2-
propanol, or chloroform.
The reaction proceeds in different planes thus
ensuring a minimum of steric hindrances. The
prevailing direction of the addition is apparently
governed by the electronic effects. For instance, the
nitrogen atom possessing the higher nucleophilicity is
primarily coordinated to the dipolarophile and thus
directs the total reaction path leading to the formation
of adducts 1-R2-2,4-diphenyl-8-(4-methylphenyl)-
2,3,7-triazaspiro[4.4]-non-8-en-6-ones I–VIII.
1-(2-Chlorophenyl)-8-(4-methylphenyl)-2,4-dip-
henyl-2,3,7-triazaspiro[4.4]non-3-en-1-one (I). Yield
67%, mp 171–173°С (from ethanol). IR spectrum, ν,
cm–1: 3174 (NH), 3144 (NH), 3034–2923 (CH), 1710
(C=O), 1535 (C–N). 1Н NMR spectrum, δ, ppm: 2.41 s
(3H, CH3), 4.26 s (1H, CH), 4.35 s (1H, CH), 6.43 s
(1H, =CH), 7.08–7.75 m (18Н, Ar), 8.12 s (1H, NH),
8.47 s (1H, NH). 13С NMR spectrum, δ, ppm: 21.9,
42.5, 45.0, 46.0, 92.1, 121.3–151.8, 167.1. Found, %:
С 75.53; Н 5.24; N 8.37. C31H26ClN3O. Calculated, %:
C 75.68; Н 5.33; N 8.54.
Hence the reaction of 3-arylmethylidene-3Н-pyrrol-
(furan)-2-ones with diarylhydrazone follows the route
of [3+2]-cycloaddition involving the exocylic С=С
bond resulting in the formation of a single product,
spiropyrazoles I–VIII.
EXPERIMENTAL
IR spectra were registered on an IR Fourier
spectrophotometer FSM 1201 from pellets with KBr. 1Н
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 5 2014

ARYLMETHYLENE-3Н-FURAN(PYRROL)-2-ONES
661
1-(2-Chlorophenyl)-2,4,8-triphenyl-2,3,7-triazas-
piro[4.4]non-3-en-1-one (II). Yield 65%, mp 165–
167°С (from ethanol). IR spectrum, ν, cm–1: 3156
(NH), 3126 (NH), 2957–2837 (CH), 1702 (C=O), 1530
3177 (NH), 3141 (NH), 3019–2974 (CH), 1718 (C=O),
1531 (C–N). Н NMR spectrum, δ, ppm: 4.21 s (1H,
1
CH), 4.27 s (1H, CH), 6.61 s (1H, =CH), 7.28–8.11 m
(18Н, Ar), 8.15 s (1H, NH), 8.37 s (1H, NH). 13С
NMR spectrum, δ, ppm: 22.5, 42.7, 46.9, 47.9, 92.9,
124.8–153.8, 168.3. Found, %: С 73.50; Н 5.34; N
11.61. C30H24N4O3. Calculated, %: C 73.76; Н 4.95; N
11.47.
1
(C–N). Н NMR spectrum, δ, ppm: 4.18 s (1H, CH),
4.42 s (1H, CH), 6.57 s (1H, =CH), 6.89–7.42 m (19Н,
Ar), 8.21 s (1H, NH), 8.53 s (1H, NH). 13С NMR
spectrum, δ, ppm: 22.5, 41.5, 43.7, 45.0, 92.3, 122.3–
150.1, 170.1. Found, %: С 75.44; Н 5.02; N 9.03.
C30H24ClN3O. Calculated, %: C 75.38; Н 5.06; N 8.79.
1-(2-Hydroxy)-8-(4-methylphenyl)-2,4-diphenyl-
7-oxadiazaspiro[4.4]non-3-en-1-one (VII). Yield
64%, mp 161–163°С (from chloroform). IR spectrum,
ν, cm–1: 3125 (NH), 3028–2965 (CH), 1757 (C=O),
8-(4-Methylphenyl)-1,2,4-triphenyl-2,3,7-triaza-
spiro[4.4]non-3-en-1-one (III). Yield 69%, mp 174–
173°С (from i-PrOH). IR spectrum, ν, cm–1: 3171
(NH), 3145 (NH), 3027–2929 (CH), 1712 (C=O), 1537
1
1580 (C–N). Н NMR spectrum, δ, ppm: 2.41 s (3H,
CH3), 4.18 s (1H, CH), 4.37 s (1H, CH), 6.89 s (1H,
=CH), 7.21–8.12 m (18Н, Ar), 8.12 s (1H, NH). 13С
NMR spectrum, δ, ppm: 23.9, 44.5, 47.9, 48.5, 93.5,
120.4–147.5, 175.6. Found, %: С 74.01; Н 5.16; N
8.37. C31H25N3O4. Calculated, %: C 73.94; Н 5.00; N
8.34.
1
(C–N). Н NMR spectrum, δ, ppm: 2.47 s (3H, CH3),
4.19 s (1H, CH), 4.54 s (1H, CH), 6.71 s (1H, =CH),
7.18–7.74 m (19Н, Ar), 8.17 s (1H, NH), 8.43 s (1H,
NH). 13С NMR spectrum, δ, ppm: 23.1, 41.1, 46.1,
47.8, 90.3, 123.4–150.6, 163.9. Found, %: С 81.48; Н
6.06; N 9.02. C31H27N3O. Calculated, %: C 81.37; Н
5.95; N 9.18.
1-(2-Chlorophenyl)-2,4,8-triphenyl-7-oxadia-
zaspiro[4.4]non-3-en-1-one (VIII). Yield 69%, mp
169–171°С (from ethanol). IR spectrum, ν, cm–1: 3159
1-(3,4-Dimethoxyphenyl)-8-(4-methylphenyl)-
2,4-diphenyl-2,3,7-triazaspiro[4.4]non-3-en-1-one
(IV). Yield 54%, mp 167–169°С (from i-PrOH). IR
spectrum, ν, cm–1: 3173 (NH), 3123 (NH), 3032–2934
(CH), 1715 (C=O), 1534 (C–N). 1Н NMR spectrum, δ,
ppm: 2.45 s (3H, CH3), 3.77 s (3H, CH3), 3.85 s (3H,
CH3), 4.20 s (1H, CH), 4.43 s (1H, CH), 6.77 s (1H,
=CH), 7.11–7.54 m (17Н, Ar), 8.12 s (1H, NH), 8.32 s
(1H, NH). 13С NMR spectrum, δ, ppm: 21.7, 42.5,
44.7, 46.4, 92.5, 119.4–148.8, 165.4. Found, %: С
76.43; Н 5.96; N 8.27. C33H31N3O3. Calculated, %: C
76.57; Н 6.04; N 8.12.
1
(NH), 3024–2938 (CH), 1756 (C=O), 1577 (C–N). Н
NMR spectrum, δ, ppm: 4.08 s (1H, CH), 4.46 s (1H,
CH), 6.87 s (1H, =CH), 7.11–7.85 m (18Н, Ar), 8.06 s
(1H, NH). 13С NMR spectrum, δ, ppm: 21.3, 43.8,
46.0, 48.3, 92.1, 120.6–152.0, 171.4. Found, %: С
75.18; Н 4.81; N 5.53. C30H23СlN2O2. Calculated, %:
C 75.23; Н 4.84; N 5.85.
This work was carried out under the financial
support of the Russian Foundation for Basic Research
(grant no. 13-03-00318).
REFERENCES
1-(3-Nitrophenyl)-8-(4-methylphenyl)-2,4-
diphenyl-2,3,7-triazaspiro[4.4]non-3-en-1-one (V).
Yield 67%, mp 175–177°С (from chloroform). IR
spectrum, ν, cm–1: 3184 (NH), 3137 (NH), 3025–2963
(CH), 1721 (C=O), 1527 (C–N). 1Н NMR spectrum, δ,
ppm: 2.41 s (3H, CH3), 4.22 s (1H, CH), 4.37 s (1H,
CH), 6.57 s (1H, =CH), 7.26–8.12 m (18Н, Ar), 8.12 s
(1H, NH), 8.35 s (1H, NH). 13С NMR spectrum, δ,
ppm: 23.9, 43.5, 45.5, 47.7, 93.4, 126.5–158.3, 169.3.
Found, %: С 74.13; Н 5.24; N 11.03. C31H26N4O3.
Calculated, %: C 74.09; Н 5.21; N 11.15.
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