Journal of the Iranian Chemical Society

, Volume 11, Issue 1, pp 17–25 | Cite as

Intramolecular interactions in nitroamines studied by 1H, 13C, 15N and 17O NMR spectral and quantum chemical methods

  • Ryszard Gawinecki
  • Erkki Kolehmainen
  • Robert Dobosz
  • Hossein Loghmani Khouzani
  • Subramanian Chandrasekaran
Original Paper


1H, 13C, 15N and 17O NMR chemical shifts are used for the characterization of the intramolecular interactions in several nitramines of the Me2N-G-NO2 type. The charge of lone electron pair of the amino group in N,N-dimethylnitramine, N,N-dimethyl-2-nitroethenamine, N,N-dimethyl-p-nitroaniline, 4-nitro-β-dimethylaminostyrene, 4-N,N-dimethylamino-β-nitrostyrene, 4-(N,N-dimethylamino)-4′-nitrobiphenyl, and 4-(N,N-dimethylamino)-4′-nitrostilbene is transferred not only to the nitro oxygens, but also to the vinylene and benzene carbons of the G spacer and to N-methyl carbons as well. Decreased nuclear shielding is found to be qualitatively related to the decreased atomic charge around a nucleus. This finding was further verified and quantified by comparison of the NMR data with those obtained by ab initio quantum chemical calculations. 17O NMR chemical shift changes seem to be more significant when the interacting NMe2 and NO2 groups are separated by a short spacer. On the other hand, 15N NMR chemical shifts suggest that a decrease of the charge at the amino nitrogen is not related to the length of the spacer alone. A lack of the linear dependence between the 17Onitro and 15Namino chemical shifts suggests that the charge lost by the amino nitrogen was only partially gained by the oxygens in the nitro group. The increased shieldings of the aryl carbons in 4-(N,N-dimethylamino)-4′-nitrobiphenyl indicate that atoms of the p,p-biphenylene spacer also gain some charge originating from the amino nitrogen. 3JH,H spin–spin coupling constant shows that among different vinylene compounds, the charge transfer to the nitro group is practically effective only in N,N-dimethyl-2-nitroethenamine where the bond between the vinylene carbons is significantly of low order by character. The calculated Natural Population Analysis (NPA) data confirms that except the nitro oxygens, other atoms that receive the negative charge lost by NMe2 in the compounds studied are the aryl and N-methyl carbons.


Nitroamines Resonance interaction Charge transfer Molecular structure Ab initio calculations 


The separation of various electron-donors and electron-acceptors by the conjugated π-electron spacer stabilized by resonance results in the nonlinear optical (NLO) response [1]. Large application possibilities of such push–pull systems in various photonic technologies deserve the structures of this type of compounds to be carefully studied [2]. Therefore, intramolecular interactions in such systems have been studied for a long time [3, 4, 5, 6, 7, 8, 9, 10, 11].

Among various more common electron-donors and electron-acceptors, Me2N and NO2 groups are the extreme cases and thus a molecule bearing both of them, Me2N-G-NO2, is a classical push–pull system. Generally, an elongation of the spacer G was found to weaken the conjugation between the NMe2 and NO2 groups [8]. However, it is still effective in 4-N,N-dimethylamino-β-nitrostyrene and it is argued to be responsible for stacking of such molecules in dimers and tetramers with antiparallel dipoles [12]. Similar aggregation was observed for the Brooker’s merocyanine structurally related to (E)-N,N-dimethyl-4-(4-nitrostyryl)benzeneamine [13], which is a resonance hybrid weighed toward a zwitterionic form even when dissolved in solvents of low dielectric constant [14].

Although significance of the intramolecular charge transfer in the push–pull compounds has not been exhaustively analyzed [15, 16], the through-resonance structure of p-nitroanilines (Scheme 1) seems to be very important from the structural point of view. However, X-ray data reveal that contribution of that form in N,N-diethyl-p-nitroaniline is only 12.7 %, which means that the other resonance structures are also important [17]. Other studies have also proved that the net π-electron population in this molecule is relatively low [18, 19].
Scheme 1

Through-resonance structure of N,N-diethyl-p-nitroaniline

According to the valence bond theory, the negative charge from the amino group in p-nitroaniline is transferred merely to the benzene ring than to the nitro group [20]. So, in spite of the criticism towards the basic concept of intramolecular charge transfer [15, 16], this phenomenon seems still to be important factor that affects the molecular structure. Recent findings [17, 18, 19, 20] suggest, however, that this hypothesis should be more or less modified.

X-ray and electron diffraction structural data show that a significant amount of the charge from the amino nitrogen in N,N-dimethylnitramine, N,N-dimethyl-2-nitroethenamine, N,N-dimethyl-p-nitroaniline, 4-nitro-β-N,N-dimethylaminostyrene and 4-N,N-dimethylamino-β-nitrostyrene was transferred to the nitro group [21]. Effectiveness of the ground-state charge transfer in N,N-dimethylnitramine was found to be very high. This effect is much weaker in 4-N,N-dimethylamino-β-nitrostyrene. An electron donating power of the amino nitrogen atom in 4-N,N-dimethylamino-β-nitrostyrene is weaker than in 4-nitro-β-N,N-dimethylaminostyrene although these two compounds are isomers. NPA shows that charge transfer from the amino to nitro oxygen atoms is again very effective in N,N-dimethylnitramine, Me2N-NO2. The oxygens of NO2 are not the only acceptors of the negative charge lost by the amino nitrogen atom. In addition to the nitro oxygens, the negative charge acceptors are the vinylene, benzene as well as N-methyl carbons.

Multinuclear magnetic resonance spectroscopy is a very powerful tool in structural studies [22, 23, 24, 25, 26]. The spectral parameters supported by the results of ab initio calculations can be very helpful for example in explaining the factors which control the charge transfer in the push–pull compounds. Since intramolecular interactions in nitroamines are not exhaustively analyzed; therefore, a series of compounds of general formula Me2N-G-NO2 (Scheme 2) has been investigated in the present paper. For the sake of convenience, numbers of atoms present in the common molecular fragments of 17 were always the same (Scheme 2).
Scheme 2

Formulas of the compounds studied and numbering of heavy atoms in their molecules

Results and discussion

Amine nitrogen in nitroamines is the source of the negative charge. The resonance interactions in 1 resulting in the charge transfer from the amino to the nitro group increases the contribution of the resonance form 1b (Scheme 3) decreasing the electron density at the amino nitrogen atom and causing deshielding in 15N NMR chemical shift (Table 1).
Scheme 3

Charge transfer in the molecule of N,N-dimethylnitroamine

Table 1

1H, 13C, 15N and 17O NMR chemical shifts (δ/ppm) for 0.1–0.2 M solutions of 17 in DMSO-d6 and in CDCl3 (in italic) at 303 K [3J(1H,1H)/(Hz) values are given in parentheses]










8.04 (9.5)

7.94 (9.0)

8.27 (9.0)

8.18 (9.0)

8.09 (9.4)

8.02 (8.9)

8.24 (9.0)

8.20 (8.8)


6.75 (9.5)

7.26 (9.0)

7.87 (9.0)

7.77 (9.0)

6.58 (9.4)

7.14 (8.9)

7.68 (9.0)

7.58 (8.8)


6.75 (10.6)

5.17 (13.5)

8.02 (13.3)

7.12 (16.5)

6.56 (10.6)

5.14 (13.4)

7.96 (13.4)

7.23 (16.2)


8.23 (10.6)

7.47 (13.5)

7.96 (13.3)

7.43 (16.5)

8.06 (10.6)

7.02 (13.5)

7.49 (13.4)

6.96 (16.2)


7.67 (8.9)

7.68 (9.0)

7.51 (9.0)

7.42 (9.0)

7.57 (9.0)

7.47 (8.7)


6.75 (8.9)

6.83 (9.0)

6.74 (9.0)

6.68 (9.0)

6.83 (9.0)

6.78 (8.7)



3.18, 2.85a







3.15, 2.82a


























































































44.84 38.04a







37.98 35.43a

















































a 17O NMR spectra were recorded for 1 M solutions in CD3CN at 348 K and in CDCl3 at 323 K (in italics) and chemical shifts are referenced to an external H2O at 0.0 ppm

aTwo N-methyl groups are not equivalent (see “Discussion”)

bSignal of this quaternary carbon atom was not observed

cOverlapped with the residual signal of the solvent

dNot observed due to the limited solubility in DMSO-d6

eNot observed due to insufficient solubility in CDCl3 and in CD3CN

The charge transfer in N,N-dimethylaniline is expected to be insignificant [δ(15N15 = −337.7 ppm in CDCl3] [27]. However, an insertion of the strong electron acceptor p-nitro group into its molecule resulting in formation of compound 3 deshields N15 considerably (Table 1). As can be seen in Table 1, δ(15N15) varies significantly throughout the series. On the other hand, δ(15Nnitro) is much less sensitive to the spacer (Table 1). It is known that δ(15Nnitro) possesses low inherent sensitivity to the substituent [28] owing to the mutual canceling of the changes of principal components of the chemical shift tensor of the nitro group [29]. Some other explanations have also to be considered. Thus, charge transfer from the amino nitrogen to nitro oxygen atoms (see, e.g., the resonance structure in Scheme 1) may not affect the nitro nitrogen itself. However, decreased C1–N18 bond lengths in 3 and 4 [21], as compared to the averaged CAr–NO2 distance [30], prove that the nitro group in these nitroarenes is really conjugated with the aromatic moiety.

The sensitivity of 17O NMR chemical shifts in meta- and para-substituted nitrobenzenes is rather low [31]. 17O NMR resonance of nitromethane (605 ppm from external H2O [32]) is deshielded when compared with the shifts of 17 (Table 1). Thus, electron density around the nitro oxygens in 17 is higher than that in nitromethane (no significant transfer of the charge to the oxygen atoms is expected to take place in its molecule). The difference of δ(17O) for 5 (561.0 ppm, Table 1) and β-nitrostyrene, Ph–CH=CH–NO2, (578.8 ppm [33]) show the same trend as the difference of δ(17O) of NH2 and NO2 substituted benzenes being close to 40 ppm [34]. Although decreased nuclear shieldings (larger chemical shifts) are usually associated with lower atomic charges [35], the correlations of these two parameters are usually fortuitous. Linear dependence between them may be treated as rational only in a narrow range of similar compounds [35]. Keeping in mind this warning, we would like to see at least how the 17O NMR chemical shifts change in 17 and such an analysis is worthy to be done, even if the found relationship has a qualitative character only. Moreover, this approach can be verified by comparison of conclusions that neglect the above warning with these based on, e.g., molecular geometries [21].

δ(17O) (Table 1) suggests that the charge at NO2 in 17 to be more significant when the interacting groups, i.e., NMe2 and NO2, are separated by the shorter spacer. On the other hand, δ(N15) (Table 1) reveal that decrease of the charge at NMe2 is not simply related to the length of the spacer. As it is shown by its correlation coefficient (0.927, CDCl3), linear dependence between the chemical shifts of O18 and N15 is rather low. Thus, one can see that the charge lost by N15 was only partially gained by O18.

A comparison of δ(17O) for 4-(N,N-dimethylamino)-4′-nitrobiphenyl, 6, (Table 1) and 4-nitrobiphenyl [32] shows that the dimethylamino group shields the C11/13, C3/5 and C4 atoms by 16.43, 1.62 and 1.66 ppm, respectively. These chemical shift differences show that the charge from the NMe2 group in 6 was transferred mainly to C11/13, C3/5 and C4.

3JH,H coupling constant for trans-RCH=CHR′ (12–18 Hz [35]) depends on the order of the vinylene carbon–carbon bond. Low values of 3JH7,H8 = 10.6 Hz (Table 1, 10 Hz [36]) for (E)-N,N-dimethyl-2-nitroethenamine, 2, supports intramolecular charge transfer of the O2N–CH=CH–NMe2 ↔ O2N=CH–CH=NMe2 type to take place [36] (JHa,Hb = 9–13 Hz for the >C=CHa–CHb=C< system [35]). As it is indicated by the coupling constants for 4 and 5 (Table 1), the respective bond in their molecules is significantly more double by character. Thus, the charge transfer in these two compounds is less effective than in 2. Comparison of the 3JH7,H8 values for 4 and 5 (Table 1) with these for β-nitro- and β-(dimethylamino)styrenes (both are equal to 13.9 Hz [37, 38]) suggests that effect of the p-NO2 and p-NMe2 groups on the magnitude of the intramolecular charge transfer in 4 and 5 is insignificant. Interestingly, effects of the β-NO2 and β-NMe2 substitution on 3JH7,H8 in styrene are comparable. Influences of the p-NO2 and p-NMe2 substituents on this coupling constant in styrene (ca. 18 Hz [39, 40]) and stilbene (ca. 16 Hz [41, 42]) are also similar. Large 3JH7,H8 coupling constant show that there is an almost fully double bond between C7 and C8 in compound 7 and in 4-nitro- and 4-dimethylaminostilbenes. Thus, effectiveness of the charge transfer in these three compounds seems to be very low.

Intramolecular charge transfer in 17 (Scheme 4) is expected to increase the Me2N–C bond order. Shortening of this bond in some nitroamines was really observed [21]. Hindering of free rotation of the dimethylamino group in 2, 4, 5 and 7 makes two N-methyl groups nonequivalent.
Scheme 4

Charge transfer in different N,N-dimethylnitroamines

1H and 13C NMR spectral data (Table 1) show that it is the case only in 2 where the charge is much more effective than in 4, 5 and 7. The X-ray data taken from literature show that Me2N–C bond in 2 [36] is really much shorter than in 3 [43, 44], 4 [45] and 5 [12], being in all of them similar. Nonequivalent N-methyl groups were also found in some related compounds. Thus, due to increased contribution of the p-O2N=C6H4=N–CH=NMe2 quinoid form, two different 1H N-methyl signals are observed in the NMR spectrum of N,N-dimethyl-N-(4-nitrophenyl)formamidine below the coalescence temperature [46].

The NMR data of 17 are expected to be in some way related to the changes in molecular geometry. An examination shows that δ(15N15)s do depend linearly neither on the calculated (Table 2) nor the experimental [21] ∠C3C4C5 in 3 and 4 and ∠C11C12C13 in 57, nor on values of ∠C6N1C2 in 37. Such a dependence was also found for neither the C16N15C17 nor O18N18O18′ bond angles. On the other hand, δ(15N15)s are proportional to the calculated and experimental lengths of the C4–N15, C8–N15 and C12–N15 as well as C1–N18 bonds (Table 2).
Table 2

Correlations between 15N15 NMR chemical shifts and geometrical parameters [bond lengths (pm) and valence angles (deg)] for compounds 17










∠C3C4C5 or C11C12C13
































d(C8N15) or d(C12N15)

















Calculated values (geometry optimized at B3LYP/6-31G(2d,p) level with PCM model of solvation. Solvent: DMSO)

aCorrelation coefficient for linear dependence δ(15N) vs various parameters. NMR chemical shifts are those of the DMSO solutions



An ab initio level of theory using the Gauge-Including Atomic Orbitals (GIAO) [34] approach seems to be very convenient method to calculate the nuclear shielding [47] for 17. Our experiences [48, 49, 50] show that these calculations predict the experimental chemical shifts well although very sophisticated basic functions are not used. The reliability of this procedure is usually high for 13C NMR shifts. On the other hand, 15N NMR chemical shifts of non-quaternary nitrogen atoms are known to be sensitive to the solvent, concentration and temperature [28]. For similar reasons, one would expect the 17O NMR chemical shifts to depend strongly on the solvent. Since the protons are always located on the periphery of the molecule, they are also subjected to more efficient intermolecular (solvent–solute) effects than the carbon atoms [51]. The calculated 15N chemical shifts for 17 performed with different B3LYP methods are in agreement with experimental data; the correlation coefficients varying between 0.96 and 1.00 (see Supporting Information). It is noteworthy that the order of the calculated δ(15N15)s are 1 > 2 > 3 > 4 > 5 > 6 > 7. Thus, electron density at the amino nitrogen is expected to be lowest and highest in 1 and 7, respectively.

Among different methods used, B3LYP/6-31G(2d,p)//M05/6-31G(d,p) was found to give the best results in comparison with the experimental 17O chemical shifts (see Supporting Information). Coefficients of the linear correlations between the calculated and experimental data (solutions in CD3CN and CDCl3) for five correlated points [δ(17O)s were available only for the limited number of compounds, see Table 1] slightly exceed 0.8. It is noteworthy that δ(17O) change in the following order: 1 < 2 < 3 < 4 < 5 < 6 < 7. Thus, both the calculated and experimental values of δ(17O) show that electron density at the nitro oxygen atoms in 1 is significantly higher than in 27 further suggesting that the gain of the charge in 1 is more efficient than in 27.

Since the δ(15N15) and δ(17O18) do change neither parallel nor monotonously in 17 (Table 1), one can assume that the charge from N15 is transmitted not only to O18 but also to other sites of the molecule. The calculated NPA data [52, 53] show that the amount of the charge left at N15 in compound 1 is much lower than in compounds 25 [21] as well as in 6 and 7 (Table 3). Notwithstanding two positively charged nitrogen atoms in 1b (Scheme 3) are bound to each other, contribution of that resonance structure seems to be higher than that of 1c.
Table 3

Natural Population Analysis (NPA) charges at the heavy atoms in compounds 6 and 7



























































Respective data for 15 are in [21]

As this can be seen in our recent paper [40] and in Table 3, except O18 other atoms that accept the negative charge lost by N15 in the molecules of compounds 27 are C3, C5, C7, C9, C10, C11, C13 and C14. Relatively high NPA values for the methyl carbon atoms, C16 and C17, are also noteworthy.

Mulliken population analysis of the total and π electron densities at the oxygen and nitrogen atoms in NO2 of nitrobenzenes were earlier found independent on the substitution [30]. The calculated NPA charges at N18 and O18 (Table 3) show this to be the rule also for compounds 3, 4, 6 and 7 which all are substituted nitrobenzenes. Interestingly the C1–N18 bonds in the molecules of compounds 3 and 4 [21] are relatively shorter than the averaged CAr–NO2 distances [28]. This suggests that the nitro group in nitramines possessing an aromatic spacer is really conjugated with the aryl moiety.


Although the classical concept of intramolecular charge transfer needs some modification, it is still an important factor that affects molecular structure of the Me2N-G-NO2 type nitroamines. Both the 1H, 13C, 15N and 17O NMR chemical shifts, and 3JH,H spin–spin coupling constants are indicative of the charge donors and acceptors in the molecule (results of the ab initio calculations show that correlation between the nuclear shieldings and atomic charges are not fortuitous). Thus, lone electron pairs of the amino nitrogen in N,N-dimethylnitramine, N,N-dimethyl-2-nitroethenamine, N,N-dimethyl-p-nitroaniline, 4-nitro-β-dimethylaminostyrene, 4-dimethylamino-β-nitrostyrene, 4-(N,N-dimethylamino)-4′-nitrobiphenyl and 4-(N,N-dimethylamino)-4′-nitrostilbene are transferred not only to the oxygens in NO2 but also to the vinylene, benzene and N-methyl carbons. The calculated Natural Population Analysis (NPA) values show that the amount of the charge at the amino nitrogen in N,N-dimethylnitramine is much lower than in other compounds (where it is almost constant). Since the above findings are consistent with those drawn from molecular geometries, the nuclear shieldings in this series of nitroamines can at least qualitatively be related to the atomic charges.


Melting points were measured on a Boetius table and are uncorrected. (E)-N,N-dimethyl-2-nitroethenamine, 2; N,N-dimethyl-4-nitroaniline, 3; 4-(N,N-dimethylamino)-4′-nitrobiphenyl, 6 and (E)-4-(N,N-dimethylamino)-4′-nitrostilbene, 7 are commercial products. N,N-Dimethylnitramine (dimethylnitramide), 1, was obtained by nitrodephosphorylation of hexamethylphosphoramide [54]. Other compounds studied were prepared according to the modified literature methods.

(E)-4-Nitro-β-(N,N-dimethylamino)styrene, 4. Mixture of p-nitrotoluene (13.72 g, 0.1 mol), N,N-dimethylformamide dimethyl acetal (15.49 g, 17.2 mL, 0.13 mol) and N,N-dimethylformamide (10 mL) was refluxed for 2 h under N2. In order to remove the unreacted p-nitrotoluene, dry residue obtained after evaporation of the solvent under diminished pressure was extracted with two 20-mL portions of 18 % hydrochloric acid. The combined extracts were made alkaline with conc. aqueous sodium hydroxide and the precipitated solid was recrystallized from methanol. The product (13.50 g, 62 %) melts at 137.5–139.5 °C (lit. mp 137–139 °C [55], 132–133 °C [56]).

(E)-4-(N,N-Dimethylamino)-β-nitrostyrene, 5. Mixture of p-(N,N-dimethylamino)benzaldehyde (7.46 g, 0.05 mol), nitromethane (4.88 g, 3.84 mL, 0.08 mol), ammonium acetate (2.31 g, 0.03 mol) and glacial acetic acid (20 mL) was refluxed for 2 h. The cold reaction mixture was poured on the crushed ice (100 mL), the precipitated solid filtered off and recrystallized from methanol twice. The product (6.63 g, 69 %) melts at 176–180 °C (lit. mp 182–183 °C [52], 179–180.5 °C [57]).

1H, 13C and 15N NMR experiments were run with a Bruker Avance DRX 500 spectrometer equipped with an inverse 5-mm-diameter probe head with a z-gradient for 0.1–0.2 M DMSO-d6 and CDCl3 solutions at 303 K. Acquisition and processing parameters of the NMR experiments are those reported earlier [58]. 2D pulsed field z-gradient (PFG) selected 1H,13C HMQC and 1H,13C HMBC experiments were run to assign reliably the 13C NMR spectra [11]. 1H and 13C chemical shifts were referenced to an internal TMS, δ = 0.0 ppm. 15N NMR chemical shifts (referenced to an external neat 15N-natural abundance nitromethane, δ = 0.0 ppm) were obtained with the PFG 1H,15N HMBC experiments [58]. 17O NMR spectra were recorded with a Varian Inova 500 MHz NMR spectrometer for 1 M solutions in CD3CN at 348 K and in CDCl3 at 323 K. 17O NMR signals are referenced to external neat 17O-natural abundance water, δ = 0.0 ppm.

Natural population analysis [52, 53] was performed using MP2/6-31G(2d,p) method for the isolated molecules (vacuum) with Gaussian 03 [59]. Molecular geometries were optimized at the B3LYP/6-31G(2d,p) level (no intermolecular interactions were considered). The frequencies were calculated to make sure that geometry is in the energy minimum (no imaginary frequencies). HF/3-21G, M05/6-31G(d,p), MP2/6-31G(2d,p) and B3LYP/6-31G(d,p) geometries were used for the GIAO computations [60] using the B3LYP functional and various basis sets (see Supporting Information).



We are very much indebted to the CI TASK Gdańsk for supply of computer time and providing programs. The authors thank Spec. Lab. Technician Reijo Kauppinen for his help in the NMR experiments. This work was supported by Polish Ministry of Science and Higher Education (Grant No. IP2011 010171).

Supplementary material

13738_2013_269_MOESM1_ESM.docx (27 kb)
Supplementary material 1 (DOCX 27 kb)


  1. 1.
    P.N. Prasad, D.J. Williams, Introduction to nonlinear optical effects in molecules and polymers (Wiley, New York, 1991)Google Scholar
  2. 2.
    G. Park, Ch. Sup Ra, B. Rae Cho, Amine donors in nonlinear optical molecules: methyl and phenyl substitution effects on the first hyperpolarizability. Bull. Korean Chem. Soc. 24, 1671–1674 (2003)CrossRefGoogle Scholar
  3. 3.
    H.A. Staab in Einführung in die Theoretische Organishe Chemie; Verlag Chemie, Weinheim, chapter 3, 1962Google Scholar
  4. 4.
    J.Y. Lee, K.S. Kim, B.J. Mhin, Intramolecular charge transfer of π-conjugated push–pull systems in terms of polarizability and electronegativity. J. Chem. Phys. 115, 9484–9489 (2001)CrossRefGoogle Scholar
  5. 5.
    J. Stals, The chemistry of aliphatic unconjugated nitramines. II. Intramolecular properties and crystal packing. Aust. J. Chem. 22, 2505–2514 (1969)CrossRefGoogle Scholar
  6. 6.
    Sz. Roszak A theoretical study of the N,N-dimethylnitramine structure. J. Mol. Struct. Theochem. 304, 269–272 (1994)Google Scholar
  7. 7.
    M.G. White, R.J. Colton, T.H. Lee, J.W. Rabalais, Electronic structure of N,N-dimethylnitramine and N,N-dimethylnitrosamine from X-ray and UV electron spectroscopy. Chem. Phys. 8, 391–398 (1975)CrossRefGoogle Scholar
  8. 8.
    B.J. Duke, A theoretical investigation of nitramine structures. J. Mol. Struct. 50, 109–114 (1978)CrossRefGoogle Scholar
  9. 9.
    R. Gawinecki, B. Stanovnik, A. Valkonen, E. Kolehmainen, B. Ośmiałowski, R. Dobosz, A. Zakrzewska, Effect of vinylene and 1,4-phenylene spacers on efficiency of the ground-state intramolecular charge-transfer in enlarged 4-dimethylamino-1-methylpyridinium cations. Struct. Chem. 20, 655–662, (2009)Google Scholar
  10. 10.
    B.V. Lopatin, Spectra and interactions of the amino and nitro groups in the molecule of nitramide. Teor. Eksper. Khim. 13, 530–533 (1977) [Theor. Exper. Chem. 13, (1977), 399–402]Google Scholar
  11. 11.
    M.A. Leiva, R.G.E. Morales, Bridge effect of the C=C, C=N and N=N bonds on the long distance electronic charge transfer of para-substituted stilbenoid compounds. Spectroscopy 14, 259–267 (2000)CrossRefGoogle Scholar
  12. 12.
    L. Hamdellou, O. Hernandez, J. Meinnel, 4-Dimethylamino-β-nitrostyrene and 4-dimethylamino-β-ethyl-β-nitrostyrene at 100 K. Acta Cryst. C62, o557–o560 (2006)Google Scholar
  13. 13.
    J.O. Morley, R.M. Morley, A.L. Fitton, Spectroscopic studies on Brooker’s Merocyanine. J. Am. Chem. Soc. 120, 11479–11488 (1998)CrossRefGoogle Scholar
  14. 14.
    J.O. Morley, R.M. Morley, R. Docherty, M.H. Charlton, Fundamental studies on Brooker’s Merocyanine. J. Am. Chem. Soc. 119, 10192–10202 (1997)CrossRefGoogle Scholar
  15. 15.
    G.W. Wheland, Resonance theory in organic chemistry (Wiley, New York, 1955)Google Scholar
  16. 16.
    L. Pauling, The nature of the chemical bond, 3rd edn. (Cornell University Press, Ithaca, 1960)Google Scholar
  17. 17.
    T.M. Krygowski, J. Marin, Crystallographic studies of intra- and inter-molecular interactions. Crystal and molecular structure of N,N-dimethyl-4-nitro-3,5-xylidine. Structural evidence against the classical through-resonance concept in p-nitroaniline and derivatives. J. Chem. Soc. Perkin Trans. 2, 695–698 (1989)CrossRefGoogle Scholar
  18. 18.
    E. Von Nagi-Felsobuki, R.D. Topson, S. Pollack, R.W. Raft, Theoretical studies of the structures of some mono- and di-substituted benzenes. J. Mol. Struct.Theochem 88, 255–263 (1982)Google Scholar
  19. 19.
    W.F. Reynolds, P. Dais, D.W. Macintyre, R.D. Topson, S. Marriott, E. von Nagi-Felsobuki, R.W. Raft, Nature of π-electron-transfer effects in organic systems with varying π-electron demand. J. Am. Chem. Soc. 105, 378–384 (1983)CrossRefGoogle Scholar
  20. 20.
    P.C. Hiberty, G. Ohanessian, Valence-bond description of conjugated molecules. 3. The through-resonance concept in para-substituted nitrobenzenes. J. Am. Chem. Soc. 106, 6963–6968 (1984)CrossRefGoogle Scholar
  21. 21.
    R. Gawinecki, E. Kolehmainen, R. Dobosz, Structure based evaluation of the resonance interactions and effectiveness of the charge transfer in nitroamines. Struct. Chem. 22, 1379–1383 (2011)CrossRefGoogle Scholar
  22. 22.
    S. Berger, S. Braun, H.O. Kalinowski, NMR spectroscopy of the non-metallic elements (Wiley, New York, 1997)Google Scholar
  23. 23.
    E. Breitmaier, Structure elucidation by NMR in organic chemistry: a practical guide Third revised edition (Wiley, Chichester, 2003)Google Scholar
  24. 24.
    R. Marek, A. Lyčka, 15N NMR spectroscopy in structural analysis. Curr. Org. Chem. 6, 35–66 (2002)Google Scholar
  25. 25.
    R. Marek, A. Lyčka, E. Kolehmainen, J. Toušek, E. Sievänen, 15N NMR Spectroscopy in structural analysis, an update 2001–2005. Curr. Org. Chem. 11, 1154–1205 (2007)Google Scholar
  26. 26.
    W.G. Klemperer, 17O-NMR spectroscopy as a structural probe. Angew. Chem. Int. Ed. Engl. 17, 246–254 (1978)CrossRefGoogle Scholar
  27. 27.
    A. Zakrzewska, R. Gawinecki, E. Kolehmainen, B. Ośmiałowski, 13C-NMR based evaluation of the electronic and steric interactions in aromatic amines. Int. J. Mol. Sci. 6, 52–62 (2005)CrossRefGoogle Scholar
  28. 28.
    G.C. Levy, R.L. Lichter, Nitrogen-15 nuclear magnetic resonance spectroscopy (Wiley, New York, 1979)Google Scholar
  29. 29.
    G.H. Penner, G.M. Bernard, R.E. Wasylishen, A. Barrett, R.D. Curtis, A solid-state nitrogen 15NMR and ab initio study of nitrobenzenes. J. Org. Chem. 68, 4258–4264 (2003)CrossRefGoogle Scholar
  30. 30.
    K.B. Lipkowitz, A reassessment of nitrobenzene valence bond structures. J. Am. Chem. Soc. 104, 2647–2648 (1982)CrossRefGoogle Scholar
  31. 31.
  32. 32.
    D.W. Boykin, A.L. Baumstark, P. Balakrishnan, A. Perjéssy, P. Hrnciar, 17O NMR studies on 4- and 4′-substituted chalcones and p-substituted β-nitrostyrenes Spectrochim. Acta. 40A, 887–891 (1984)Google Scholar
  33. 33.
    D.J. Craik, G.C. Levy, R.T.C. Brownlee, Substituent effects on nitrogen-15 and oxygen-17 chemical shifts in nitrobenzenes: correlations with electron densities. J. Org. Chem. 48, 1601–1606 (1983)CrossRefGoogle Scholar
  34. 34.
    M.In. Kaupp, M. Kaupp, M. Bühl, V.C. Malkin, (eds) Calculations of NMR and EPR parameters, theory and applications, chap 18 (Wiley-VCH, Weinheim, 2004), pp 293–306Google Scholar
  35. 35.
    R.M. Silverstein, T.C. Morrill, G.C. Bassler, Spectrometric identification of organic compounds; 5th edn. (Wiley, New York, 2005) p 221Google Scholar
  36. 36.
    A. Hazell, A. Mukhopadhyay, Structure of a push-pull olefin: trans-N,N-dimethyl-2-nitroethenamine. Acta Cryst. B36, 747–748 (1980)CrossRefGoogle Scholar
  37. 37.
    S.E. Denmark, B.S. Kesler, YCh. Moon, Inter- and intramolecular [4+2] cycloadditions of nitroalkenes with olefins. 2-Nitrostyrenes. J. Org. Chem. 57, 4912–4924 (1992)CrossRefGoogle Scholar
  38. 38.
    M.C. Caserio, R.E. Pratt, R.J. Holland, The nature of sulfur bonding in α, β-unsaturated sulfides and sulfonium salts. J. Am. Chem. Soc. 88, 5747–5753 (1966)CrossRefGoogle Scholar
  39. 39.
    K. Yoshida, T. Koujiri, E. Sakamoto, Y. Kubo, New near infrared absorbing metal complex dyes: synthesis and metallochromic properties of two isomeric ligands, 2-(dimethylamino)naphtho [1,2-g] and [2, 1-g] quinoline-7,12-diones. Bull. Chem. Soc. Jpn. 63, 1748–1752 (1990)CrossRefGoogle Scholar
  40. 40.
    S.P. Jacober, R.P. Hanzlik, Carbon-13 and oxygen-18 kinetic isotope effects on methanolysis of p-nitrostyrene oxide. J. Am. Chem. Soc. 108, 1594–1597 (1986)CrossRefGoogle Scholar
  41. 41.
    S. Iyer, G.M. Kulkarni, C. Ramesh, Mizoroki–Heck reaction, catalysis by nitrogen ligand Pd complexes and activation of aryl bromides. Tetrahedron 60, 2163–2172 (2004)CrossRefGoogle Scholar
  42. 42.
    R. Wang, B. Twamley, J.M. Shreeve, A highly efficient, recyclable catalyst for C–C coupling reactions in ionic liquids: pyrazolyl-functionalized N-heterocyclic carbene complex of palladium(II). J. Org. Chem. 71, 426–429 (2006)CrossRefGoogle Scholar
  43. 43.
    O.Ya. Borbulevych, R.D. Clark, A. Romero, L. Tan, M.Yu. Antipin, V.N. Nesterov, B.H. Cardelino, C.E. Moore, M. Sanghadasa, T.V. Timofeeva, Experimental and theoretical study of the structure of N,N-dimethyl-4-nitroaniline derivatives as model compounds for non-linear optical organic materials. J. Mol. Struct. 604, 73–86 (2002)Google Scholar
  44. 44.
    T.W.C. Mak, J. Trotter, The crystal and molecular structure of N,N-dimethyl-p-nitroaniline. Acta Cryst. 18, 68–74 (1965)CrossRefGoogle Scholar
  45. 45.
    A.A. Tishkov, A. D. Dilman, V,I. Faustov, A.A. Birukov, K.S. Lysenko, P.A. Belyakov, S.L. Ioffe, Yu.A. Strelenko, M.Yu. Antipin, Structure and Stereodynamics of N,N-Bis(silyloxy)enamines. J. Am. Chem. Soc. 124, 11358–11387 (2002)Google Scholar
  46. 46.
    J.P. Marsh, L. Goodman, A novel solvent effect in the nmr spectra of some N,N-dimethylformamidines. Tetrahedron Lett., pp 683–688 (1967)Google Scholar
  47. 47.
    I. Ando, G.A. Webb, Theory of NMR parameters (Academic Press, London, 1983)Google Scholar
  48. 48.
    B. Ośmiałowski, E. Kolehmainen, R. Gawinecki, R. GIAO/DFT calculated chemical shifts of tautomeric species. 2-Phenacylpyridines and (Z)-2-(2-hydroxy-2-phenylvinyl)pyridines. Magn. Reson. Chem. 39, 334–340 (2001)CrossRefGoogle Scholar
  49. 49.
    E. Kolehmainen, A. Zakrzewski, A. Zakrzewska, M. Nissinen, B. Ośmiałowski, R. Gawinecki, Predominance of amino-sulfonyl hydrogen bonding in (Z)-2-benzene-sulfonyl-phenyl-2-(phenylhydrazono)ethanones in crystals and in solution: an experimental NMR and X-ray crystallographic and theoretical ab initio and DFT-GIAO studies. Polish J. Chem. 77, 31–45 (2003)Google Scholar
  50. 50.
    H. Loghamni-Khouzani, T. Rauckyte, B. Ośmiałowski, R. Gawinecki, E. Kolehmainen, GIAO/DFT 13C NMR chemical shifts of 1,3,4-thiadiazoles. Phosph. Sulf. Silicon 182, 2217–2225 (2007)CrossRefGoogle Scholar
  51. 51.
    A.M. Barfield, P. Fagerness, Density functional theory/GIAO studies of the 13C, 15N, and 1H NMR chemical shifts in aminopyrimidines and aminobenzenes: relationships to electron densities and amine group orientations. J. Am. Chem. Soc. 119, 8699–8711 (1997)CrossRefGoogle Scholar
  52. 52.
    F. Benington, R.D. Morin, L.C. Clark, Mescaline analogs. V. p-Dialkylamino-β-phenethylamines and 9-(β-aminoethyl)julolidine. J. Org. Chem. 21, 1470–1472 (1956)Google Scholar
  53. 53.
    A.E. Reed, L.A. Curtiss, F. Weinhold, Intermolecular interactions from a natural bond orbital, donor–acceptor viewpoint. Chem. Rev. 88, 899–926 (1988)CrossRefGoogle Scholar
  54. 54.
    J.C. Bottaro, C.D. Bedford, R.J. Schmitt, D.F. McMillen, Synthesis of N,N-dimethylnitramine by nitrodephosphorylation of hexamethylphosphoramide. J. Org. Chem. 53, 4140–4141 (1988)CrossRefGoogle Scholar
  55. 55.
    H. Bredereck, G. Sinchen, R. Wahl, Orthoamide, VIII Über die Umsetzung aktivierter Methylgruppen an substituierten Toluolen und Heterocyclen mit Aminal-tert.-butylester zu Enaminen. Chem. Ber.101, 4048–4056 (1968)Google Scholar
  56. 56.
    M.G. Vetelino, J.W. Coe, A mild method for the conversion of activated aryl methyl groups to carboxaldehydes via the uncatalyzed periodate cleavage of enamines. Tetrahedron Lett. 35, 219–222 (1994)CrossRefGoogle Scholar
  57. 57.
    D.E. Worrall, L. Cohen, p-Dimethylamino derivatives of nitrostyrene. J. Am. Chem. Soc. 66, 842–842 (1944)Google Scholar
  58. 58.
    E. Kolehmainen, B. Ośmiałowski, T.M. Krygowski, R. Kauppinen, M. Nissinen, R. Gawinecki, Substituent and temperature controlled tautomerism: multinuclear magnetic resonance, X-ray, and theoretical studies on 2-phenacylquinolines. J. Chem. Soc. Perkin Trans II, 1259–1266 (2000)CrossRefGoogle Scholar
  59. 59.
    M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J. A Montgomery, T. Vreven Jr., K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q.Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision E.01, (Gaussian, Inc., Pittsburgh, 2004)Google Scholar
  60. 60.
    K. Woliński, J.F. Hinton, P. Pulay, Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J. Am. Chem. Soc. 112, 251–8260 (1990)Google Scholar

Copyright information

© Iranian Chemical Society 2013

Authors and Affiliations

  • Ryszard Gawinecki
    • 1
  • Erkki Kolehmainen
    • 2
  • Robert Dobosz
    • 1
  • Hossein Loghmani Khouzani
    • 3
  • Subramanian Chandrasekaran
    • 4
  1. 1.Department of ChemistryUniversity of Technology and Life SciencesBydgoszczPoland
  2. 2.Department of ChemistryUniversity of JyväskyläJyväskyläFinland
  3. 3.Department of Chemistry, Faculty of SciencesUniversity of IsfahanIsfahanIran
  4. 4.Department of ChemistryGeorgia State UniversityAtlantaUSA

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