Научная статья на тему 'Atropoisomerism in a series of N-arylimides of norbornane dicarboxylic acids'

Atropoisomerism in a series of N-arylimides of norbornane dicarboxylic acids Текст научной статьи по специальности «Химические науки»

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Аннотация научной статьи по химическим наукам, автор научной работы — Salakhov M.S., Bagmanov B.T., Mustafayeva F.A.

Using the physico-chemical methods of analysis the atropoisomerism in a series of N-arylimides of norbornane dicarboxylic acids has been determined and confirmed by quantum-mechanical calculations and Stuart-Briegleb models

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Текст научной работы на тему «Atropoisomerism in a series of N-arylimides of norbornane dicarboxylic acids»

UDC 547.398.3+542.9551



M.S.Salakhov, |B.T.Bagmanov |, F.A.Mustafayeva

Institute of Polymer Materials, NAS of Azerbaijan salahov_mustafa@mail.ru Received 22.10.2015

Using the physico-chemical methods of analysis the atropoisomerism in a series of N-arylimides of norbornane dicarboxylic acids has been determined and confirmed by quantum-mechanical calculations and Stuart-Briegleb models.

Keywords: N-arylimides, norbornane dicarboxylic

mation, ortho-effect.

In organic molecules plane structure fragments combined with each other by a single bond, because of that they cannot be in movement of rotation across of bond connecting these groups form conformational isomerism -atropoisomerism [1, 2]. In this case the Van der Waals radius of ortho-substitutes in plane structure fragments been large enough, the free rotation capabilities of the same groups with regard to the bond bonding them are limited, in the case of such "inhibitor" ortho-substitutes are not present because of the conformers access energy to each other is reduced enough plane structures are free conformational along the bond bonding their nuclear - spatial isomerism is replaced by conformational events [3, 4].

By using a variety of physico-chemical methods in N-arylimides of norbornan dicarboxylic acid spatial structure details, we which of investigated [5, 6] formation of various confor-mers as a result of the rotation both with planar structure five-membered imide group and phenyl ring along the N-C bond which unites them is consistent with the view of conformational analysis. The stability of these conformers will depend on imide groups in endo- or exo-position compared to the bicyclo[2.2.1]heptan and pyramidal structure of the nitrogen atom created stereochemical features, also number, size, structure properties, electron nature and position of the inhibitor substitutes in phenyl ring.

When analysing NMR-spectra of N(o-me-thoxy phenyl)imides of 5,6-dihydroxy-endo- and exo-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid

acids, stereochemistry, atropoisomerism, confor-

(BHDA) we found first clearly bifurcation of peaks belonging to the OCH3 group in ortho-iso-mer, being singlet in meta- and para-isomers, we have explained its reason by the rotation difficulty along the N-C bond in ortho-isomers [7-9].

The studies have shown that the presence of the specific stereochemically natured OCH3 group (radius 0.145 nm) in ortho-position of N-arylimides of norbornane dicarboxylic acid, as well as the pyramidal shaped geometric structure of the nitrogen in imide group is the cause of covering methoxy group with the carbonyl group of the imide group and creates "obstacle" during the intramolecular rotation and therefore the above-mentioned compound is available as optically active compound. However, the lack of the polyracemation period of the appropriate compounds (at 170C 2.5 min) does not allow to obtain optically active isomers individually [10].

On the basis of this fact it can be inferred that in case of o-position there is one substitute then for obtaining stable optically active isomers selection of functional groups with more large-scale (for example, Br-, COOH-, NO2- etc.) is important, because it is known that in this case even hydrogen atoms of other circle does not allow to free rotation [11, 12]. However, there are scientific studies confirming racemation of all atropoisomers saved in the required conditions formed by the presence of only a substitute on ortho-position in each plane structure [13].

Stabile optically active compounds will be formed at the moment, when in the molecule four large-scale groups pairs on different planes will be in barrier position to each other [14].

8 7 6 5 4 3 2 1 0 PP"»

8 7 6 = 4 3 2 1 0 f>P"»

8 7 6 S 4 3 2 1 o ppm

Fig. 1. NMR-spectra of /rans-5,6-dihydroxy-e«do-BHDA N(o-, m-, _p-methoxyphenyl)imides.

In this case there appear enantiomers, found in compounds not connected with asymmetric atom and compounds such as allenes, spirans, adamantanes, biphenyls, as well as in like compounds in which carbon atoms are replaced with stereo chemical similar heteroatom. At atropoisomerism case that we observe in N-arylimides of norbornane carboxylic acids

the role of such heteroatoms plays tetrahedral structure nitrogen atoms at sp3 hybrid state. There at the rotation of five-membered imide group with phenyl ring around the N-C bond through the pyramidal structure of the N atom reason of spatial obstruction between carbonyl groups in imide group with the methoxy group of the unique geometric structure at ortho-

position in phenyl ring forming stable conformational isomerism - atropoisomerism and it shows itself in bifurcation of peaks NMR-spectra about a methoxy group (Figure 1).

If we want to visualize atropos structures of N(o-methoxy phenyl) imides of 5,6-dihydroxy-eftdo-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, then it should be noted the possibility of two different - favorable and unfavorable side spatial structures and being sin- and anti-conformationals (a,b,c,d) of methoxy fragments in each of this structures (Figure 2).

Only (b) state from the sin- (a) and anti-

(b) conformations in unfavourable structure is possible, because the overlap of CO group with OCH3 group makes the variant (a) impossible, but in favolable structure both of possible sin-

(c) and anti- (d) variants may be available and

probably the diversity of intensities of the singlet's belonging to the metoxy group is just result of this.

On the other hand, if singlet magnetic anisotropy compatible to the low intensity (b) structure is far away from C=O group, in easy convertible to each other (c) and (d) structures the methoxy- group protons are often shadowed by carbonyl groups. Therefore, the signals inherent to more intensive (c) and (d) structures are displaced toward the more powerful area. It should be noted that the ratio of disadvantage (b) and advantage (c and d) structures are in ratio of 25% to 75% to the integral intensity, it also coincides with theoretical perceptions when conformational characteristics are taken into consideration.

\ ^ C —'

yC N „


H-C^ I


(b) anti-

(c) sin- (d) anti-

Fig. 2. Possible side conformations of N(o-methoxy phenyl)imides of 5,6-dihydroxy-endo-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid.

Generation of 5,6-diols with trans-stuc-ture as result of dihydroxylation of N-substitute imides of norbornenedicarboxylic acid on the base of aromatic amines is confirmation in IR spectra by the presence of the specific strips in area of 3465-3480 cm-1 (hydrogen bonds between molecules). In this case in IR spectra at 3520 cm-1 and in higher areas are not found strips express the intramolecular H-bond: it was also confirmed that the decreases of the concentration of solutions prepared on the base of these products in chloroform, the intensity of lanes reflecting the H-bond between molecules is also reduced and appears lanes with specific frequency characteristic of the free hydroxyl groups (3620-3640 cm-1).

On the base of delicate structure analysis it was approved that the N-substituted imides of 5,6-dihydroxy BHDA are in endo- or exo-struc-ture. Thus, constant of spin-spin interaction (0-2 h) of H5 and H6 atoms in endo-isomer with H1 and H4, smaller than in corresponding exo-isomers (2-4 h). Corresponding endo- and exo-isomers can be also classified with taking into conside-

7 7

ration H bridge protons: in endo-isomers H protons (0.9 ppm) are displaced to the more powerful area even in suitable exo-isomers (1.15 ppm).

The bifurcation of signals (3.75 and 3.80 ppm) belonging to the OCH3 group in the NMR-spectra of dihydroxylation of N(o-, m-, p-me-thoxyphenyl) and N(o-, m-, p-tolyl)imides of 5,6-dihydroxy norbornane dicarboxylic acids, but failure to observe such bifurcation in corresponding tolyl imides is the evidence of the being in an unequal positions of metoksil group.

With quantum-mechanical researches it was determined that in the case of the free activation enthalpy AG of the organic molecules in the absence of at least 65-85 kC/mol atropoisomers are stable as individual enan-tiomer [15]. To obtain namely the individual atropoisomers we have synthesized N-arylimides BHDA with using aromatic amines substituted on o,o'-positions with voluminous atoms (Br) and groups (OCH3), the model studies that we have conducted for them being suitable in terms of the approval of the results of physico-che-

mical research, also allowed to take some of the generalizations.

The similar studies on Stuart-Briegleb models of mono- and bis- imides formed by reaction of bromine derivatives of 3,3'-dimethoxy 4,4'-diaminodiphenylmethane with endo- and exo-BHDA confirm that the presence of in aromatic ring OCH3 group and Br atom on o,o'-positions comparison with nitrogen atom ensures stability of the enantiomer form - voluminous OCH3 and Br groups of phenyl ring and carbonyl groups of the plane structure imide group prevents racemation creation and provides creating individual optical isomers (Figure 3).

The presence of the tetrahedral carbon atoms in these type compounds a result of rotational motion of phenyl ring comparison with it provide availability being molecule in the form of two side conformers "face to face" and "pseudo perpendicular". In each of side conformers the sin- and anti-positions of imide group it is possible that their stability, on the one hand, is connected with spatial and electron factors, on the other hand, with the interactions of the functional groups (amide-, hydroxyl-, carbonyl-, halogen-, methoxy-) in the molecule.

Model analysis shows that in both states of "the face to face" conformer (sin- and anti-) the norbornane rings and functional groups attached to them (in our case hydroxyl groups) are sufficiently distant and do not participate in intramolecular interaction effects (eg., H-bond) (Figure 4). In this case, the functional groups are free and active, relevant structures gain access to react easily in both directions (eg., polycondensation). We must note the formation of "globular" conformer due to creating of H- bond in maximum approaching of hydroxyl groups in "Pseudo perpendicular" structure. In this case, as the molecule is in the least energic and the most stable state, the functional groups are in the "spending" state, its including to the reaction is relatively difficult. The noted results are of great interest for identifying use opportunities of "spatial structure - property" connections for future chemical transformations.



"Pseudo perpendicular"


anti-"Face to face"

Fig. 3. Photos of dihydroxy-BHDA bisimides on the base of 3,3'-dimetoxy-5,5'-dibromo-4,4'-diaminodiphenylmetane.

With being large scale bromine atoms and methoxy-group in 0,0'-positions of the phenyl ring regardless of the imide groups in endo- and exo-positions in N-arylimides of NBDA, as well as in their epoxy and dihydroxy derivatives the limited possibilities of rotation of these fragments around of the N-C bond of phenyl ring seems manifestly in models. Due to pyramidal structure of the nitrogen atom regardless of location imide groups on endo- or exo-positions in compared to bicyclo-hepten ring, if the functional groups located on ortho-positions of phenyl ring are single, it will be on sin-, or on anti-position, in this case the spatial size of the radicals determine the easy or difficult transition of these structures. We have seen it clearly on an example of methoxy group. When both of o,o'-positions of phenyl ring are captured with voluminous atom or groups it is about single enantiomer structure. There are not sin- and anti-isomers and the conformational opportunities is limited completely. The above-mentioned structure details are clearly observed on models,

confirmed by the physico-chemical analysis and quantum-chemical calculations.

Making the quantum-chemical calculation there have been found full energy, formation of energy, the total energy of the isolated atoms, the electronic energy, the mutual influence energy of atom groups, formation heat, the conversion energy of the system [16, 17].

The quantum-chemical calculation results of N-arylimides of endo- and exo-BHDA show that (Table 1), in this series passing from N-phenylimides to N-(o-, m-, ^-substitute phenyl) imides depending on substituted electron character (electron donor CH3-, OCH3-,Cl- or electron acceptor NO2-, COOH-) and position (o-, m-, p-) energy indicators are changed as follows: passing from the in series of from the N-phenylimides to the N-arylimides with electron donor (CH3-, OCH3-,Cl-) and electron acceptor (NO2-, COOH-) substitutes except of formation heat (Qfh) other calculated energy indicators reduced comply with the law. The comparative reconciliations of the formation heat

with the structure changes has enabled to substantiate many details in this area [18, 19].

The formation heat of the N-phenylimides of endo- and exo-BHDA is higher than that of the corresponding compounds with the electron donor substitutes in meta- and para-positions. But in corresponding N-arylimides with electron acceptor substitutes the value of the Qfh is higher than the N-phenylimides. However, regardless of the electron nature in the corresponding orto-isomers there is observed as rule an abnormally sharp increase (approximately twice) in value of Qfh. For example, if in N(o-methoxyhenyl)imides of endo-and exo-BHDA Qfh is properly equal to 89.54 and 88.78 kcal/mol, in meta-isomers it is 45.94 and 46.33 kcal/mol, in para-isomers it is 46.26 and 45.84 kcal/mol. This fact is changes in a similar manner for the N(chlorine phenyl)-, N(nitro phenyl)-, N(carboxy phenyl) imides of endo- and exo-BHDA too. If approach from the delicate structure analysis view this "ortho-effect" can be explained from the atropoisomerism process which is observed in NMR-spectrum. In isomers with the same all other quantitative and qualitative indexes and differ only the positions of radicals in aromatic ring (o-, m-, p-) formation of difference in quantum-chemical indexes is the indicator of the formation of big trouble in rotation around the N-C bond in ortho-isomers, and it is basically bonding with the spatial factors and it is favorable from point of view determination of proper isomer and for the allow to synthesis of enantiomer individual compounds. On the other hand, from point of view of coordination of Qfh with the structure the above-mentioned result being important, can be a guiding factor for the synthesis of optical compounds with the known properties.

As a result research into N-substituted arylimides of norbornan dicarboxylic acid there can be mentioned the following:

- Experimental and theoretical studies show that regardless of the endo- and exo-structures in all o-substituted N-arylimides of norbornene dicarboxylic acid there rotation goes on with difficulty around the N-C bound.

- Depending on the size and the electron nature of the radical in phenyl ring in some

cases (e.g., in N-o-metoxyimide Qfh 89.54 and 88.78 kcal/mol) racemation is going easy, whereas in other case there are formed stable spatial isomers (eg., in o-chloro-phenylimide Qfh - 137.95 and 137.48 kcal/mol or o-nitrophenylimide 148.86 and 150.49 kcal/mol).

- The final stage in the formation of separately sin- and anti-isomers is the formation of intermediate complex of this or other configuration, depending on what amide acid and imide on suitable structure, are obtained.

- Delicate structure research of synthesized compounds opens up new opportunities for the creating "spatial structure-property" bonds for the study chemical conversion of these compounds.

Experimental part

All of the synthesized compounds are in solid state. Their composition and structure are determined on the basis of physicochemical analysis.

The delicate structure of new synthesized compounds are confirmed by the modern physico-chemical analysis methods, quantum-mechanical calculations and Stuart-Briegleb models. As model compound here was taken N-(methoxyphenyl)imides of norbornene dicarboxylic acid, it is affordable option for the solution of many problems connected with spatial structure.

The purity of the synthesized compounds is controlled by TLC method on "sulifol"; meantime as the solvent taken from a mixture ben-zene:chloroform:acetic acid in volume ratio of 5:4:1. The detection of spots were carried out by mercury lamp with ultra-violet radiation [20]. The melting temperatures of newly synthesized compounds' were determined by the element analysis, molecular formula were found.

The NMR spectra at Tesla BS-487 device, in 80 MHz frequency, in CDCl3 [21, 22], IR spectra at "UR-20" device in vaseline oil in the form of slurry in 400-3800 cm-1 area, UV spectra at "Specord M-40" spectrophotometer in 180-400 nm area, in ethanol solution (concentration 10-4 mol/l, kuwait size 1 cm) were taken [23].

endo- endo- "face to face"

Fig. 4. The "face to face" and "Pseudo perpendicular" structures of the endo-endo-configuration BHDA bis-imides on the base of 3,3'-dimetoxy-5,5'-dibromo-4,4'-diaminodiphenylmetane.

The synthesis of mono- (or bis-imides)

was carried out directly and also on the basis of mono- (or bis-) amides:

a) Mono- (or bis-) amide acids have been imidized as follows: 0.01 mol amide acid is melted by heating and kept at this temperature for 1-1.5 h. As a result of dehydration obtained mono- (or bis-) imides are crystallized in the mixture of benzene-normal heptane. Recrystallization is continuing in an ethanol solution. Yield of mono- (or bis-)imides - 83.1-96.5%.

b) Mono- (or bis-) amide acids are heated at 100±5°C temperature in sodium acetate dissolved acetic anhydride up to 40% for the 2-2.5 hours. Then the mixture is cooled to room temperature and is poured into the icy water. The formed crystalline compound is filtered, washed with distilled water several times, dried and

analysed. Yield mono- (or bis-)imides is 86-96%.

c) Appropriate 0.01 mol amine dissolved in 100 ml DMFA is poured into three-necked flask fitted with a mixer and in the solvent boiling temperature (1520C) the solution of 0.01 mol (or 0.02 mol) anhydride in 100 ml DMFA are added with drops. Then the mixture is heated 5-6 h, left to cool. The mixture cooled to room temperature is poured into the icy water, kept for 12 hours. Crystalline compound separated by filtration, washed several times with distilled water, crystallized from benzene: n-heptane (1:1 ratio) mixture. Yield mono- (or bis-)imides 90.8-96.4%. IR spectrum, Av, cm-1; C=O (1640-1646), C=C (1690-1710). The epoxidation of mono- (or bis-) imides was carried out in the following way:

0.01 mol N-arilimide is dissolved in 15 ml

dioxane and at 8-100C the solution of 10 ml peracetic acid in dehydrated dioxane is added with uninterruptedly cooling (100C). After the use of peracetic acid completely (3.5-4 h) acetic acid is expelled with water pump vacuum, the reaction product is crystallize from waterless benzene. Yield is 87-90%.

The dihydroxylation of mono- (or bis-) imides was carried out in the following ways: a) Directly oxidation of mono- (or bis-) imides with peracetic acid. 0.01 mol N-arilimide is dissolved in 30 ml acetic acid, 1-2 drops of concentrated H2SO4 are added and 10 ml H2O2 (30% solution) in the 10 ml acetic acid mixture added into solution with uninterruptedly mixing. The

mixture is mixed at 700C for 2 h. Then, 15 ml of water is added to the reaction mixture and is heated for 1 h. The crystals formed at the end of the reaction are filtered, washed with water and crystallized from the ethanol. The properties of trans-dihydro-xyimides are shown in the Table 2. b) The hydrolysis of corresponding epoxy compounds. 0.01 mol N-arilimide of 5,6-exo-epoxybicyclo[2.2.1]heptane endo- and exo-2.3-dicarboxylic acid in 30 ml H2SO4 (5% solution) is heated at 600C. The reaction product is filtered, washed with distilled water and dried. Yield of trans-dihydroxyimide is 78-90%.

№ Compound Full energy, kcal/mol Full energy, a.u.* Formation energy, kcal/mol Isolated atom energy, kcal/mol Electron energy, kcal/mol Nuclear interaction energy, kcal/mol Heat of formation, kcal/mol

1 endo- BHDA anhydride -50419.82 -80.35 -2072.89 -48346.93 -251580.14 201160.3 60.61

2 exo-BHDA anhydride -50418.52 -80.35 -2071.60 -48346.93 -249381.14 118962.62 61.91

3 N-(phenyl)imide of endo-BHDA -66962.30 -106.71 -3400.07 -63562.23 -442170.58 375208.28 72.72

4 N-(phenyl)imide of exo-BHDA -66961.64 -106.71 -3399.41 -63562.23 -437799.29 370837.65 73.39

5 N-(o-methoxyphenyl)imide of endo-BHDA -77693.32 -123.81 -3717.90 -73975.42 -547051.29 469357.97 89.54

6 N-(o-methoxyphenyl)imide of exo-BHDA -77694.08 -123.81 -3718.66 -73975.42 -544515.96 463821.88 88.78

7 N-(ra-methoxyphenyl)imide of endo-BHDA -77736.93 -123.88 -3761.50 -73975.42 -529660.67 451923.74 45.94

8 N-(ra-methoxyphenyl)imide of exo-BHDA -77737.54 -123.88 -3762.19 -73975.19 -534702.21 456964.67 46.33

9 N-(p-methoxyphenyl)imide of endo-BHDA -77737.62 -123.88 -3762.19 -73975.42 -527149.39 449411.77 46.26

10 N-(p-methoxyphenyl)imide of exo-BHDA -77737.03 -123.88 -3761.61 -73975.42 -522233.81 444496.78 45.84

11 N-(o-chlorophenyl)imide of endo-BHDA -74563.03 -118.82 -3311.69 -71251.34 -495794.34 421231.31 137.95

12 N-(o-chlorophenyl)imide of exo-BHDA -74563.50 -118.82 -3312.16 -71251.34 -490957.26 416393.76 137.48

13 N-(ra-chlorophenyl)imide of endo-BHDA -74636.90 -118.94 -3385.56 -71251.34 -483504.95 408868.05 64.08

14 N-(ra-chlorophenyl)imide of exo-BHDA -74636.14 -118.94 -3384.80 -71251.34 -478852.81 4041216.67 64.85

15 N-(p-chlorophenyl)imide of endo-BHDA -74636.51 -118.94 -3385.17 -71251.34 -481193.99 406557.48 64.48

16 N-(p-chlorophenyl)imide of exo-BHDA -74635.76 -118.94 -3384.42 -71251.34 -476582.47 401946.71 65.22

17 N-(o-nitrophenyl)imide of endo-BHDA -85288.66 -135.91 -3527.96 -81760.70 -586389.84 501101.17 147.85

18 N-(o-nitrophenyl)imide of exo-BHDA -85264.65 -135.88 -3503.95 -81760.70 -590681.86 505417.21 148.86

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19 N-(ra-nitrophenyl)imide of endo-BHDA -85263.02 -135.87 -3502.32 -81760.70 -564994.13 479731.12 142.49

20 N-(ra-nitrophenyl)imide of exo-BHDA 85269.68 -135.88 -3508.98 -81760.70 -559840.80 474571.12 143.83

21 N-(p-nitrophenyl)imide of endo-BHDA 85274.12 -135.89 -3513.42 -81760.70 -558489.01 473214.89 139.39

22 N-(p-nitrophenyl)imide of exo-BHDA 85273.42 -135.89 -3512.72 -81760.70 -553421.24 468147.82 140.09

23 N-(o-carboxy phenyl) imide of endo-BHDA -84250.12 -134.26 -3770.12 -80480.01 -595111.87 510861.74 -7.31

24 N-(o-carboxy phenyl) imide of exo-BHDA -84248.93 -134.27 -3768.93 -80480.01 -587032.55 502783.62 -6.12

25 N-(ra-carboxy phenyl) imide of endo-BHDA -84258.38 -134.27 -3778.38 -80480.01 -563406.90 479148.52 -15.57

26 N-(ra-carboxy phenyl) imide of exo-BHDA -84253.39 -134.26 -3773.38 -80480.01 -559563.68 475310.30 -10.58

27 N-(p-carboxy phenyl) imide of endo-BHDA -84287.17 -134.32 -3807.16 -80480.01 -549520.08 465232.91 -44.36

28 N-(p-carboxy phenyl) imide of exo-BHDA -84254.77 -134.27 -3774.76 -80480.01 -552529.32 468274.54 -11.96

* atomic unit

Table 1. Quantum chemical calculation indexes of endo- and exo-BHDA anhydride and N-phenyl, N-(metoxy-)phenyl, N-(chloro -)phenyl, N-(nitro -)phenylimides

Table 2. Physico-chemical parameters of the synthesized new compounds


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M.S.Salahov, B.T.Bagmanov , F.O.Mustafayeva

Norbornandikarbon tur§ulan N-arilimidlarinda atropoizomerliyin varligi fiziki-kimyavi analiz usullan ila muayyan olunmu§, kvant-mexaniki hesablamalar va Stuart-Briqleb modellari vasitasila tasdiq edilmi§dir.

Agar sozfor:norbornandikarbon tur§ulari N-arilimidbri, stereokimya, atropoizomerlik, konformasiya, orto-effekt.




, Ф.А.Мустафаева

Физико-химическими методами анализа определена атропоизомерия в ряду М-арилимидов норборнандикарбоновых кислот и подтверждено квантово-механическими расчетами и моделями Стюарта-Бриглеба.

Ключевые слова: N-арилимиды норборнандикарбоновых кислот, стереохимия, атропоизомерия, конформация, oрто-эффект.

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