1993 cycloaddition reactions cycloaddition reactions O 0070 34 -068 Reaction Potentiality of N-Aryldichloromaleimides in Diene Reactions with Cyclopentadiene and 1,3-Cyclohexadiene. -Kinetic parameters of cycloaddition reaction of a number of N-aryldichloromaleimides such as (I) with cyclopentadiene and cyclohexadiene are investigated. -(NAGIEV, YA. M.; SAKUILOVA, YA. D.; BAGIROV, SH. T.; SHNULIN, A. N.; ADIGEZALOV, V. A.; NASIBOV, SH. S.; PASHAEV, B. K.; SHAKHTAKHTINSKII, T. N.; Zh.
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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