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Russian Journal of Organic Chemistry 2023, 59, 652-655
Russian Journal of Organic Chemistry 2023, 59, 652-655
, 2023.
Russian Text © The Author(s), 2023, published in Zhurnal Organicheskoi Khimii, 2023, Vol. 59, No. 4, pp. 541–546.
Synthesis of 2-(Benzenesulfonyl)-1,1,1-tribenzylhydrazin-1-ium
Chloride and Its Heterocyclization
with Various Dipolarophiles
A. A. Makhmudovaa,*
a Azerbaijan State Pedagogical University, Baku, 1000 Azerbaijan
*e-mail: iradam@rambler.ru
Received July 12, 2022; revised July 23, 2022; accepted July 26, 2022
DOI: 10.1134/S1070428023040139
652
SYNTHESIS OF 2-(BENZENESULFONYL)-1,1,1-TRIBENZYLHYDRAZIN-1-IUM CHLORIDE 653
Scheme 1.
Ph Ph
Ph
N Ph + PhSO2NCl Na+ N Cl–
–NaCl
HN SO2Ph
Ph Ph
1
2-bromopropionic acid, 3-chloropropane-1,2-diol, and anion by the action of alkali. Elimination of water with
chloroacetonitrile afforded pyrazole derivatives 2–6 participation of the sulfonamide NH group generated
(Scheme 2). Presumably, these reactions begin with unsaturated ketone, and the subsequent cyclization via
substitution of halogen by the sulfonamido group, addition to the benzylic methylene group afforded the
followed by cyclization involving the benzylic methy- final product. Unlike acetylacetone, 4-hydroxy-4-
lene group. The 1H NMR spectrum of 1-benzenesul- methylpentan-2-one reacted with 1 to produce pyrida-
fonyl-2-benzyl-4-hydroxy-5-methyl-3-phenyl-2,3-di- zine derivative 7 (Scheme 3). Heterocyclization of 1
hydro-1H-pyrazole (3) in DMSO-d6 showed a signal at with epichlorohydrin and 1-benzenesulfonyl-2-(chloro-
δ 2.00 ppm due to methyl group, a signal at δ 3.90 ppm methyl)aziridine led to the formation of tetrahydro-
due to benzylic protons, and aromatic proton signals pyridazines 8 and 9, respectively (Scheme 4).
in the region δ 7.20–7.39 ppm with appropriate
intensities. Scheme 4.
Ph
Scheme 2.
Ph 1 + Cl Ph N
Y X
Ph N
X N PhSO2 XH
1 + R2 R1
N 8, 9
R1 PhSO2
R2 8, X = O; 9, X = NSO2Ph.
2–6
In the 1H NMR spectrum of N-(1-benzyl-6-phenyl-
2, R1 = CH2NHSO2Ph, R2 = H; 3, R1 = OH, R2 = Me; 4, R1 =
CH2OH, R2 = Me; 5, R1 = COMe, R2 = Me; 6, R1 = NH2, R2 = H. hexahydropyridazin-4-yl)benzenesulfonamide (9),
protons of the two CH2 and two CH groups resonated
The 1H NMR spectrum of N-[(1-benzenesulfonyl- in the region δ 3.06–3.80 ppm which was obscured
2-benzyl-3-phenyl-2,3-dihydro-1H-pyrazol-4-yl)- by the solvent signal. The NH proton resonated as
methyl]benzenesulfonamide (2) showed a singlet at a doublet at δ 5.46 ppm. Aromatic protons gave rise to
δ 1.50 ppm due to methylene protons, two doublets in an unresolved multiplet in the region δ 7.02–7.56 ppm.
the region of 2.95 due to CH protons in the pyrazole The reaction of 1 with dimedone afforded indazole
ring, a signal at δ 3.60 ppm due to CH2N protons, and 10 (Scheme 5).
a doublet at δ 5.20 ppm due to NH proton. Aro-
matic proton signals were located in the region Scheme 5.
δ 7.20–7.70 ppm. O O Ph
Acetylacetone reacted with ammonium salt 1 to Ph
give pyrazole derivative 3. Presumably, the reaction 1 + N
involved initial formation of the corresponding carb- Me Me
N
O
Me Me
Scheme 3. SO2Ph
10
Ph
Me
HO Me Base Ph N EXPERIMENTAL
1 +
Me Me N
O PhSO2 The IR spectra were recorded on a Nicolet iS-10
Me
Me FTIR spectrometer (USA). The 1H NMR spectra were
7 recorded on a Tesla-BS 567 spectrometer at 90 MHz.
CONFLICT OF INTEREST 9. Omietanski, G.M. and Sisler, H.H., J. Am. Chem. Soc.,
1956, vol. 78, p. 1211.
The author declares the absence of conflict of interest. https://doi.org/10.1021/ja01587a033
10. Killer, R.N. and Smith, P.A.S., J. Am. Chem. Soc., 1946,
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