Synthesis and Properties of 3-Substituted 2 H -Chromen-2-ones
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hesis and Properties of 3-Substituted 2H-Chromen-2-ones I. V. Dyachenkoa, V. D. Dyachenkoa, P. V. Dorovatovskyb, V. N. Khrustalevc,d, and V. G. Nenaidenkoe,* a
Taras Shevchenko Lugansk National University, Lugansk, 91011 Ukraine
b
“Kurchatov Institute” National Research Center, Moscow, 123182 Russia c
d
People’s Friendship University of Russia, Moscow, 117198 Russia
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia e
Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia *e-mail: [email protected] Received April 5, 2020; revised April 7, 2020; accepted April 10, 2020
Abstract—The condensation of salicylaldehyde with CH acids [p-methoxyacetoacetanilide, ethyl 3-amino-3sulfanylidenepropanoate, 3-amino-N-aryl-3-sulfanylidenepropanamides, and ethyl 2-(1,3-thiazol-2- and -4-yl) acetates] afforded 3-substituted chromen-2-ones. Some properties of the products were studied. The structures of 3-[4-(4-chlorophenyl)-1,3-thiazol-2-yl]-2H-chromen-2-one, 2-oxo-2H-chromene-3-carboxamide, and 2-imino-N-(2-methoxyphenyl)-2H-chromene-3-carboxamide were determined by X-ray analysis. Keywords: p-methoxyacetoacetanilide, ethyl 3-amino-3-sulfanylidenepropanoate, 3-amino-N-aryl-3-sulfanylidenepropanamide, ethyl 2-(1,3-thiazol-2-yl)acetate, 2H-chromen-2-one (coumarin), X-ray analysis
DOI: 10.1134/S1070428020070015 densations of salicylaldehyde (1) with some CH acids, p-methoxyacetoacetanilide (2) and 3-amino-N-aryl-3sulfanylidenepropanamides 3 in ethanol at 20°C in the presence of triethylamine. The reaction with CH acid 2 gave 2-hydroxy-N-(4-methoxyphenyl)-2-methyl-2Hchromene-3-carboxamide 4. A probable intermediate in this transformation is Knoevenagel condensation product A which undergoes chemoselective intramolecular cyclization to final structure 4 (Scheme 1).
2H-Chromen-2-one (coumarin) derivatives exhibit various biological activities, such as fungicidal [1], antimicrobial [2, 3], and antitumor [4]. They are used as intermediate products in the synthesis of highly fluorescent dyes [5], anticoagulants [6], caspase activators and apoptosis inducers [7], as well as acetylcholinesterase inhibitors [8]. In continuation of our studies on 2H-chromen-2-one derivatives [9–11], in this work we performed con-
Scheme 1. O CHO
O
OMe
O
+ OH
Me
Me
N H
–H2O
N H
OMe
O
HO 1
2
A OMe
O
O
N H OH Me 4
1123
1124
DYACHENKO et al. Scheme 2. S S 1
+
O
H 2N
O
H 2N N H
N H
R
R
3a, 3b
HO B
O H2O, KOH
N H
R = Me
O
O
6 N H
–H2S O
Me
O
O R
NH
Me(CH2)8I (7), KOH
5a, 5b
N
R = OMe
O
OMe
NH
( )5
8
Me
3, 5, R = Me (a), OMe (b).
Scheme 3. O S 1
O
S
EtO
NH2
+ H2N
O H 2O –EtOH, –H2S
OEt
NH2 O
O
HO 9
C
Salicylaldehyde (1) reacted with CH acids 3a and 3b under similar conditions to produce N-aryl-2-imino2H-chromene-3-carboxamides 5a and 5b. Presumably, C 14
O2 C6
C5
C 15 C
C 4A
4
C3
C9
N2
C
C 13
10
C 12 C
C7 C8
C
8A
O1
C2
N1
11
O3 C 16
Fig. 1. Structure of the molecule of 2-imino-N-(2-methoxyphenyl)-2H-chromene-3-carbox
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