Interaction of barbituric acids with o-dialkylaminobenzaldehydes

Краснов, К. А.; Карцев, В. Г.; Khrustalev, Victor N.

doi:10.1070/mc2006v016n01abeh002216

Cited by 15 publications

(22 citation statements)

References 12 publications

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“…These values were greater than those found for our reaction, although the cyclization to give spirocyclic analogs proceeded more readily [14]. The negative value of the activation entropy obtained in our study reflected a highly organized transition state.…”

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confidence: 53%

Synthesis and Kinetics of the Cyclization of 3-(Dialkylaminophenyl)-2-(phenylcarbonyl)-prop-2-enenitriles

Platonova

Глухарева

Zimovets

et al. 2013

Chem Heterocycl Comp

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The considerable interest in tetrahydroquinolines and their derivatives is primarily due to the biological activity of tetrahydroquinolines themselves [1,2], as well as their remarkable reactivity and the variety of chemical transformations, which make these compounds convenient building blocks in the synthesis of other structures with high biological activity [3]. One method for the synthesis of tetrahydroquinoline systems is the cyclization of N,N-dialkyl-o-vinylanilines proceeding through a tert-amino effect mechanism [4][5][6][7].We studied the reaction of 2-dialkylaminobenzaldehydes 1a-i with benzoylacetonitrile (2), leading to N,N-dialkyl-o-vinylanilines 3a-i, which, in turn, cyclized to the condensed 1,2,3,4-tetrahydroquinolino-5-carbonitriles 4a-i. Examination of the literature showed that an analogous reaction has been carried out only using o-piperidinobenzaldehyde as the starting reagent [8].Knoevenagel condensation products 3a-e,h,i could not be isolated in the condensation of 2-piperidinobenzaldehydes 1a-e,h,i, since the cyclization to give 1,2,3,4-tetrahydroquinolino-5-carbonitriles 4a-e,h,i dominated under these reaction conditions [9]. Knoevenagel condensation products 3f,g, that did not undergo cyclization in toluene, were isolated only in the case of benzaldehydes 1f,g. This finding may be attributed to the lower basicity of the morpholine and piperazine dialkylamino groups. 1,2,3,4-Tetrahydroquinolino-5-carbonitriles 4f,g were obtained by the cyclization of N,N-dialkyl-o-vinylanilines 3f,g upon heating in 1-butanol at reflux. 1,2,3,4-Tetrahydroquinolino-5-carbonitriles 4a-i contain from two to four asymmetric sites.

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confidence: 53%

Synthesis and Kinetics of the Cyclization of 3-(Dialkylaminophenyl)-2-(phenylcarbonyl)-prop-2-enenitriles

Platonova

Глухарева

Zimovets

et al. 2013

Chem Heterocycl Comp

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“…It was shown by quantum-chemical calculations that the rate-limiting step was migration of a hydrogen atom, where the activation energy amounted to 29.6 kcal/mol at 90°C [69]. This value was slightly above the experimentally determined activation energy for the cyclization of ortho-vinylanilines 5 at 100°C (24.5 kcal/mol) [37]. Through an experiment with a deuterium-labeled piperidine derivative it was established [71] that the generation of allene 89 from the propargyl ester 90 was accompanied by a 1,3-migration of the acyloxy group, a 1,5-hydride shift, and cyclization to tetrahydroquinolines 91.…”

Section: -100%mentioning

confidence: 74%

“…The authors also demonstrated that condensation under mild conditions (aqueous ethanol, 50°C, 5 min [37]) allowed to isolate the intermediate vinyl derivatives 39 with yields up to 86%.…”

Section: -97%mentioning

confidence: 96%

“…During the formation of the intermediate olefin, the double bond was probably turned in such a way that the equatorial proton at the α-carbon atom was close to the double bond. It should be noted that the possibility of a π···H bond in such compounds was demonstrated [37], and this explained the low barrier to hydrogen migration from the α-carbon atom at the amino group to the double bond carbon atom [42]. Here the substituent at position 4 of the piperidine fragment was located equatorially due to the steric influence of the bulky cyclic substituent at the double bond.…”

Section: -80%mentioning

confidence: 99%

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tert-Amino effect: the Meth-Cohn and Reinhoudt reactions (Review)

Platonova

Глухарева

Zimovets

et al. 2013

Chem Heterocycl Comp

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The term "tert-amino effect" was proposed in 1972 [1] for the cyclization reactions of tertiary anilines containing various double bonds at the ortho position. Meth-Cohn and Suschitzky [1] referred to the first observation of the tert-amino effect by Pinnow in 1895 [2]. Many different examples of reactions involving the tert-amino effect have now accumulated, and it clearly is a convenient method for the synthesis of an impressive number of nitrogen-containing heterocycles that otherwise might be difficult to obtain. Reviews were published by Reinhoudt in 1990 [3] and by Meth-Cohn in 1996 [4] on heterocyclization reactions that take place by the mechanism of the tert-amino effect. Another review dedicated to 1,6-and 1,8-naphthiridine derivatives was published in 2003 by Quintela [5]. In the review [6] that we published in 2005, attention was focused on the use of such reactions for the synthesis of spiro compounds. In the review [7], published in 2006, the cyclization reactions of ortho-vinylanilines and their heterocyclic aza analogs were considered, and classification according to the method of ring formation was proposed.

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“…Spiro compounds have been reported to possess biological activities that include anti-inflammatory activity [34], anticonvulsant, CNS depressant [35], narcotic [36], hypotensive, analgesic [37]. Several works have been reported for the synthesis of other spiro barbiturates [38][39][40][41][42][43][44].…”

Section: Introductionmentioning

confidence: 99%

New spiro (thio) barbiturates based on cyclohexanone and bicyclo [3.1.1]heptan-6-one by nonconcerted [1+5] cycloaddition reaction and their conformational structures

Pesyan¹,

Noori²,

Poorhassan³

et al. 2014

Bull. Chem. Soc. Eth.

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ABSTRACT. Crossed-aldol condensation reaction of aromatic aldehydes with ketones such as; acetone and cyclohexanone leads to the efficient formation of cross conjugated α,β-unsaturated ketones in excellent yield. The intermolecular and then intramolecular Michael addition reaction of α,β-unsaturated ketones derived from acetone and cyclohexanone with (thio)barbituric acids lead to synthesis new type of 7,11-diaryl-2,4-diazaspiro[5.5]undecane-1,3,5,9-tetraone and 2,4-diaryl-1'H-spiro[bicyclo[3.3.1]nonane-3,5'-pyrimidine]-2',4',6',9(3'H)-tetraone, respectively in good yield. Structure elucidation is carried out by 1 H NMR, 13C NMR, FT-IR, UV-Visible, mass spectroscopy and X-ray crystallography techniques. A possible mechanism of the formation is discussed. The structural conformation also demonstrated by coupling constants derived from dihedral angles between vicinal and geminal protons. The 1 H NMR spectra of NH protons of spiro compounds derived from barbituric acid show a broad singlet peak instead, these protons in the spiro compounds derived from thiobarbituric acid show two distinct peaks.

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Interaction of barbituric acids with o-dialkylaminobenzaldehydes

Cited by 15 publications

References 12 publications

Synthesis and Kinetics of the Cyclization of 3-(Dialkylaminophenyl)-2-(phenylcarbonyl)-prop-2-enenitriles

Synthesis and Kinetics of the Cyclization of 3-(Dialkylaminophenyl)-2-(phenylcarbonyl)-prop-2-enenitriles

tert-Amino effect: the Meth-Cohn and Reinhoudt reactions (Review)

New spiro (thio) barbiturates based on cyclohexanone and bicyclo [3.1.1]heptan-6-one by nonconcerted [1+5] cycloaddition reaction and their conformational structures

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