Unusual One-Pot "Substitution" of 3- Acetyl and 3- Ethoxycarbonyl Functions for Cyano Group in Coumarins

Keywords: Michael reaction, 3-ethoxycarbonyl(acyl)coumarins, malonic acid dihydrazide, N'-salicylidene derivatives of coumarin-3-carboxylic acid, lactonc ring opening.Earlier we established that reaction of 3-ethoxycarbonyl(acyl)coumarins with cyanoacetylhydrazine and its N-derivatives under Michael reaction conditions leads to synthesis of 3-cyanocoumarins [1,2]. In an extension of this research, under similar conditions (ethanol, 70-75~ catalytic amounts of piperidine), we have studied the reaction of 3-cthoxycarbonyl-, 3-acetyl-, and 3-benzoylcoumarins la-c and also their 6-methyl-and 6(8)-methoxysubstituted derivatives ld-i with malonic acid dihydrazide 2. We have established that N'-salicylidene derivatives of coumarin-3-carboxylic acid hydrazide 3a-c are formed as a result of this reaction.R 4 R 4 3a.-r la R = OC2H5, R ~a = H; lb R = CH 3, R Ia = H; lc R = C6H5, R TM = H; ld R = OC2H5, R 3 = CH3, R 1"2'~ = H; le R = R e = CH3, R 1'3'4 = H; lfR = CrHs, R 2 = CH3, R 1"3"4 = H; lg R = OC2Hs, R 4 = OCH3, R t'2"3 = H; lh R = CH3, R 4 = OCH3, R t'2'3 = H; 1i R = C6H5, R 4 = OCH3, R 1'2'3 = H; 3a R t4 = H; 3b R 2 = CH3, R 1'2'3 = H; 3c R 4 = OCH3, R 1'2'3 = H D. I. Mendeleev Russian

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One-pot synthesis of N-(3-coumarinoyl-)-N′-(salicylidene)hydrazines from 3-ethoxycarbonyl-(acyl)coumarins

Nemeryuk

Dimitrova

Sedov

et al. 2000

Chem Heterocycl Compd

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Conversions of Coumarins Accompanied by Intermediate Opening and Recyclization of the Lactone Ring. 2. Study of the Interaction of Malonic Acid Hydrazide and Amide Derivatives with 3-Acyl(3-cyano, 3-ethoxycarbonyl)Coumarins

Nemeryuk

Dimitrova

Анисимова³

et al. 2005

Chem Heterocycl Compd

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Ethoxycarbonylacethydrazide reacts in an analogous manner. Special features have been studied of the interaction of malonic acid amide derivatives with unsubstituted coumarin and with coumarins containing electron-withdrawing groupings in position 3 of the ring.Keywords: 3-acyl(3-cyano, 3-ethoxycarbonyl)coumarins, malonic acid hydrazide and amide derivatives, mass spectrometric study of reaction products and reaction mixtures, opening and recyclization of the coumarin lactone ring, Michael reaction.Study of the interaction of 3-acyl(ethoxycarbonyl)coumarins with malonic acid dihydrazide under the conditions of the Michael reaction has shown that this reaction occurs analogously to the conversion of 3-acyl(ethoxycarbonyl)coumarins into 3-cyanocoumarins discovered by us previously [2, 3] with the formation of coumarin-3-carboxylic acid hydrazide 2.The resulting hydrazide 2, in its turn, interacts with the initial 3-acyl(ethoxycarbonyl)coumarins with the formation of salicylidene derivatives of coumarin-3-carboxylic acid hydrazides 4. The composition of the products essentially depends on the structure of the initial coumarin. In the case of coumarins unsubstituted in the benzene ring, and also their 6-methyl (6-Br) or 8-OMe derivatives, the salicylidene derivatives of coumarin-3-carboxylic acid hydrazides 4a-d predominate among the reaction products [4]. In the case of 3-ethoxycarbonyl(acetyl)coumarins the formation of the corresponding N,N'-biscoumarinoyl-2-hydrazines 3a-c was noted. These compounds are formed in insignificant amount and were not isolated in the pure state. Their presence in the reaction mixture was established by the presence in the mass spectra of the corresponding peaks for the molecular ions.

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Electronic structure of π-systems. Studies of electronic structures and tautomeric transformations of a series of 4-methyl-8-(R-phenylazo)dihydrofuro[2,3-h]coumarin-9-ones

et al. 2010

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Tautomeric transformations of a series of 4 methyl 8 (R phenylazo)dihydrofuro[2,3 h] coumarin 9 ones were studied by 1 H NMR, IR, electronic absorption spectroscopy, mass spectrometry, and quantum chemistry methods. The obtained results suggest that (p R phenyl) derivatives exist in the quinone hydrazone form, while (o R phenyl)derivatives exist as a mixture of quinone hydrazone and azo enol tautomers with domination of the former. The anti quinone hydrazone tautomers with a strong intramolecular hydrogen bond are more favorable than the syn quinone hydrazone tautomers.

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Unusual One-Pot "Substitution" of 3- Acetyl and 3- Ethoxycarbonyl Functions for Cyano Group in Coumarins

Cited by 7 publications

References 1 publication

One-pot synthesis of N-(3-coumarinoyl-)-N′-(salicylidene)hydrazines from 3-ethoxycarbonyl-(acyl)coumarins

One-pot synthesis of N-(3-coumarinoyl-)-N′-(salicylidene)hydrazines from 3-ethoxycarbonyl-(acyl)coumarins

Conversions of Coumarins Accompanied by Intermediate Opening and Recyclization of the Lactone Ring. 2. Study of the Interaction of Malonic Acid Hydrazide and Amide Derivatives with 3-Acyl(3-cyano, 3-ethoxycarbonyl)Coumarins

Electronic structure of π-systems. Studies of electronic structures and tautomeric transformations of a series of 4-methyl-8-(R-phenylazo)dihydrofuro[2,3-h]coumarin-9-ones

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