ChemInform Abstract: Reaction Potentiality of N‐Aryldichloromaleimides in Diene Reactions with Cyclopentadiene and 1,3‐Cyclohexadiene.

Nagiev, Ya. M.; Sakuilova, Ya. D.; Bagirov, Sh. T.; Shnulin, A. N.; Adigezalov, V. A.; Nasibov, Sh. S.; Pashaev, B. K.; Shakhtakhtinskii, T. N.

doi:10.1002/chin.199334068

Cited by 3 publications

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“…A series of calculations (vide infra) suggested that N -aryl group substitution would have a measurable impact on the relative rates of the intramolecular Diels–Alder reactions. There is limited literature on the effect of aryl substitution of N -arylanilides on Diels–Alder kinetics, even when embedded in the common N -phenylmaleimide dienophile . We thought this matter of general interest due to the relative distance between the electronically differentiated aryl group and the reactive dienophile.…”

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confidence: 99%

Domino Acylation/Diels–Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions

et al. 2015

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The development of the domino reaction between an aminoethyl-substituted diene and maleic anhydride to afford an N-substituted octahydroisoquinolin-1-one is described. A typical procedure involves the treatment of a 1-aminoethyl-substituted butadiene with maleic anhydride at 0 °C to room temperature for 20 min under low-solvent conditions, which affords a series of isoquinolinone carboxylic acids in moderate to excellent yields. NMR monitoring suggested that the reaction proceeded via an initial acylation step followed by an intramolecular Diels-Alder reaction. For the latter step, a significant rate difference was observed depending on whether the amino group was substituted by a phenyl or an alkyl (usually benzyl) substituent, with the former noted by NMR to be substantially slower. The Diels-Alder step was studied by density functional theory (DFT) methods, leading to the conclusion that the degree of preorganization in the starting acylated intermediate had the largest effect on the reaction barriers. In addition, the effect of electronics on the aromatic ring in N-phenyl substrates was studied computationally and experimentally. Overall, this protocol proved considerably more amenable to scale up compared to earlier methods by eliminating the requirement of microwave batch chemistry for this reaction as well as significantly reducing the quantity of solvent.

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Section: Resultsmentioning

confidence: 99%

Domino Acylation/Diels–Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions

et al. 2015

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“…[2,[4][5][6][7][8]. Here we report on the syntheses of new monoand bicyclic compounds proceeding from o-, m-, and p-aminobenzoic acids.…”

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Synthesis of 2,3-dichlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid N-carboxyphenylimides

Nagiev

2012

Russ J Org Chem

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A I C COOH Cl N Cl Cl O O R IVа _ IVc Compounds of bicyclo[2.2.1]hept-and [2.2.2]oct-5-ene series exhibit a wide range of biologic and physiologic action [1][2][3][4][5][6]. They are synthesized using primary amines and cyclopentadiene and 1,3-cyclohexadiene as dienes.We formerly studied the synthesis of similar compounds using as primary amines various functionally substituted amines: aminonitriles, nitramines etc. [2,[4][5][6][7][8]. Here we report on the syntheses of new monoand bicyclic compounds proceeding from o-, m-, and p-aminobenzoic acids.First we investigated the reaction of dichloromaleic anhydride (I) and aminoacids IIa-IIc giving N-arylimides of dichloromaleic acid IIIа-IIIc. In the fi rst stage of the process amidoacids А are formed [6] which under the reaction condition undergo further cyclization into the corresponding imides. Judging from the yields of compounds IIIа-IIIc the reactivity of isomeric aminobenzoic acids decreses in the series para-, meta-, ortho-due to the growing steric hindrance to the formation of the planar dichloromaleic acid N-arylimide [9].The composition and structure of synthesized compounds IIIа-IIIc were confi rmed by the elemental analysis, IR and 1 Н NMR spectroscopy. The formation of the assumed structure is indicated by the presence of groups =СО, -СООН, chlorine and tertiary nitrogen atoms. In the 1 Н NMR spectra of compounds IIIа-IIIc the proton signals are registered in the following regions, δ, ppm: 10.3 and 11.5 (СООН), 7.20 and 7.99 (С 6 Н 4 ).Synthesized dichloromaleic acid N-arylimides IIIа-IIIc possess four electron-acceptor groups resulting in their high reactivity in the diene synthesis involving cyclopentadiene.The composition and structure of synthesized adducts were confi rmed by the elemental analysis, IR and 1 Н NMR spectroscopy. In the IR spectrum of adduct IVb the absorption bands were present of the vibration of the benzene ring at 1630-1536 cm -1 and also of the stretching and bending vibrations of the С-Н bond (3000, 1440 cm -1 ). The bands in the region of 2950-2880 [δ(=CH)] and 960-820 cm -1 [δ(C-H)] indicate the presence in the molecule of a strained double bond.In the 1 Н NMR spectrum of imide IVc the protons of the six-membered ring of the norbornene fragment form a spin system АА 1 ХХ 1 where А and А 1 are protons Н 1,4 , δ 3.44 ppm, and Х and Х 1 are protons Н 5,6 , δ 6.45 ppm. The bridging methylene protons are nonequivalent and appear as an АВ system with δ(Н А ) 2.19, δ(Н В ) 2.50 ppm, R = о-СOOH (а), m-СOOH (b), p-СOOH (c).

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“…The reaction occurred in two steps with initial formation of amido acid A [8] which then underwent cyclization to imide III.…”

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“…We previously studied the Diels-Alder reaction of N-substituted dichloromaleimides with cyclopentadiene [2,[5][6][7], which led to the formation of bicyclic adducts, and examined the structure and properties of the products, as well as some general relations holding in this reaction. In continuation of studies in this line, the present communication reports on the Diels-Alder reaction of N-substituted dichloromaleimides with 1,3-cyclohexadiene.…”

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ChemInform Abstract: Reaction Potentiality of N‐Aryldichloromaleimides in Diene Reactions with Cyclopentadiene and 1,3‐Cyclohexadiene.

Cited by 3 publications

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Domino Acylation/Diels–Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions

Domino Acylation/Diels–Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions

Synthesis of 2,3-dichlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid N-carboxyphenylimides

Synthesis of N-substituted 2,3-dichlorobicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid imides

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