Structure and nonlinear optical properties of phenylazo compounds. Structural characterization of 3-amino-3-morpholinyl-2-(o-nitrophenylazo)-propenonitrile and o-nitrophenylhydrazonomalononitrile

Нестеров, В. Н.; Timofeeva, Tatiana V.; Duerksen, Gary L.; Clark, Ronald D.

doi:10.1016/s0022-2860(97)00374-8

Cited by 7 publications

(5 citation statements)

References 17 publications

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“…Therefore results of our calculations should be considered only as feasible ones. It should be mentioned, however, that for some other dimers consisting of larger and elongated molecules (for example, for 3-amino-3-morpholinyl-2-( o -nitrophenylazo)propenonitrile) the difference between the C i and C 2 dimers is more significant (∼6 kcal/mol in preference for C i dimer), and C i computed dimers were found to be very close to those found in the crystal . Similar calculations for two known NLO compounds with bulky substituents, namely, 2-(cyclooctylamino)-5-nitropiridine (COANP) and 2-(adamantylamino)-5-nitropiridine (AANP), showed the large preference of the C 2 dimers in comparison with the C i ones, and these compounds were found to form acentric crystals…”

Section: Resultssupporting

confidence: 51%

Molecular Crystal Structures and Nonlinear Optical Properties in the Series of Dicyanovinylbenzene and Its Derivatives

et al. 1998

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X-ray single-crystal structures, molecular mechanics (MM) calculations of the optimal molecular dimers, and calculations of the static second-order polarizabilities (β) were performed for a large series of methoxyand dimethylamino-substituted derivatives of dicyanovinylbenzene and some of its analogues having large values of the molecular nonlinear optical susceptibilities. X-ray structural analysis has been performed for 3,4-dimethoxy-and 3,4,5-trimethoxy-dicyanovinylbenzenes (I,Crystal packing analysis and energetic MM calculations revealed the factors responsible for the formation of the centrosymmetric crystals. Compounds III and V were found to form acentric crystal structures (space groups P2 1 and Pc, respectively) and therefore are capable to the second-harmonic generation (SHG) in solid state. Qualitative data have demonstrated that compound V is rather active in SHG in the powder state (using Nd:YAG laser with λ ) 1064 nm) that may be important for its application. On the contrary, the powder of III is not active in SHG despite the "optimal" crystal packing that might be related to the strong absorption of the second harmonic light at λ ) 532 nm, but this compound gives strong SHG signal using the laser light with λ ) 1907 nm. Analysis of the influence of the different substituents in the aromatic ring on the calculated β values in the series of the compounds studied was made.

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Section: Resultssupporting

confidence: 51%

Molecular Crystal Structures and Nonlinear Optical Properties in the Series of Dicyanovinylbenzene and Its Derivatives

et al. 1998

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“…1 H NMR spectral data are in agreement with the literature 45. According to the general procedure I, hydrazone 2a was synthesized from aniline(1.0 g, 10.73 mmol) and obtained as an orange solid(1.81 g, 99%): Mp 136-138°C (EtOH); R f 0.54 (cyclohexane-EtOAc 4 : 1); 1 H NMR δ 13.00 (br s, 1H, NH),7.49-7.45 (m, 2H, H-2, H-6), 7.45-7.39 (m, 2H, H-3, H-5), 7.26-7.18 (m, 1H, H-4);13 C NMR δ 141.3 (C-1), 129.5 (C-3, C-5), 125.8 (C-4), 116.4 (C-2, C-6), 114.3, 109.9 (2 CuN), 84.5 (CvN); IR ν 3197 (NH), 2234, 2212 (CuN), 1604, 1547, 1474, 1441, 1282; MS (ESI) m/z 169 [M − H] − .…”

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confidence: 90%

“…According to the general procedure I, hydrazone 2a was synthesized from aniline (1.0 g, 10.73 mmol) and obtained as an orange solid (1.81 g, 99%): Mp 136-138 °C (EtOH); R f 0.54 (cyclohexane-EtOAc 4 : 1); 1 H NMR δ 13.00 (br s, 1H, NH), 7.49-7.45 (m, 2H, H-2, H-6), 7.45-7.39 (m, 2H, H-3, H-5), 7.26-7.18 (m, 1H, H-4); 13 According to the general procedure I, hydrazone 2b was synthesized from 2-benzyloxyaniline (1.3 g, 6.52 mmol) and obtained as an orange solid (1.59 g, 89%): Mp 114-116 °C (EtOH); R f 0.47 (cyclohexane-EtOAc 3 : 1); 1 H NMR (acetone-d 6 ) δ 10.62 (br s, 1H, NH), 7.58-7.51 (m, 3H, H Ar ), 7. 3H,H Ar ),2H,1H,, 5.32 (s, 2H, CH 2 ); 13 C NMR (acetone-d 6 ) δ 148.1 (C-2), 137.4 (C-1′), 130.7 (C-1), 129.6 (CH), 129.1 (CH), 128.5 (CH), 127.6 (CH), 122.9 (CH), 116.9 (CH), 114.6 (CH), 113.9, 109.4 (2 CuN), 88.2 (CvN), 71.9 (CH 2 ); IR ν 3275 (NH), 2223, 2205(CuN), 1609, 1594, 1530, 1485, 1461, 1441, 1278, 1162, 1107 45 2-[(3-Benzyloxy-phenyl)-hydrazono]-malononitrile (2f ). According to the general procedure I, hydrazone 2f was synthesized from 3-benzyloxyaniline (5.0 g, 25.1 mmol) and obtained as an orange solid (6.79 g, 98%): R f 0.67 (cyclohexane-EtOAc 2 : 1); 24 2-[(3-tert-Butyl ester)-hydrazono]-malononitrile (2h).…”

Section: General Procedures V For the Synthesis Of The Pyrazolooxadia...mentioning

confidence: 99%

Microwave-assisted preparation of 4-amino-3-cyano-5-methoxycarbonyl-N-arylpyrazoles as building blocks for the diversity-oriented synthesis of pyrazole-based polycyclic scaffolds

et al. 2015

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The synthesis of 4-amino-3-cyano-N-arylpyrazoles A based on a Thorpe-Ziegler cyclization as the key step has been achieved using microwave activation. Via a new diversity-oriented synthetic pathway, these highly functionalized building blocks allowed the access to various heteroaromatic scaffolds such as pyrazolo-pyridines B, pyrazolo-pyrimidines C and pyrazolo-oxadiazoles D. Interestingly, these platforms contain three to four reactive sites that could be used for post-functionalization in order to further increase the molecular diversity.

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“…The present investigation is a continuation of a project that includes syntheses and structural studies of polar conjugated organic compounds that crystallize in non-centrosymmetric space groups (Antipin et al, 1998;Nesterov et al, 1998Nesterov et al, , 2000Nesterov, Antipin, Nesterov, Moore et al, 2004;Nesterov, Antipin, Nesterov, Penn et al, 2004). These compounds may ®nd applications in non-linear optical materials (Zyss, 1994;Kuzyk & Dirk, 1998) and in the syntheses of heterocyclic compounds (Brunskill et al, 1984;Nesterov et al, 2002).…”

Section: Commentmentioning

confidence: 97%

Polymorphism and solvolysis of 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide

Нестеров

Nesterov

2004

Acta Crystallogr C

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Two new polymorph forms, (Ia) and (Ib), of the title compound, C(14)H(17)N(3)S, and its solvate with acetonitrile, C(14)H(17)N(3)S.0.25C(2)H(3)N, (Ic), have been investigated. Crystals of the two polymorphs were grown from different solvents, viz. ethanol and N,N-dimethylformamide, respectively. The polymorphs have different orientations of the thioamide group relative to the CN substituent, with s-cis and s-trans geometry of the C=C-C=S diene fragment, respectively. Compound (Ic) contains two independent molecules, A and B, with s-cis geometry, and the solvate molecule lies on a twofold axis. The core of each molecule is slightly non-planar; the dihedral angles between the conjugated C=C-CN linkage and the phenyl ring, and between this linkage and the thioamide group are 13.4 (2) and 12.0 (2) degrees in (Ia), 14.0 (2) and 18.2 (2) degrees in (Ib), 2.3 (3) and 12.7 (4) degrees in molecule A of (Ic), and 23.2 (3) and 8.1 (4) degrees in molecule B of (Ic). As a result of strong conjugation between donor and acceptor parts, the substituted phenyl rings have noticeable quinoid character. In (Ib), there exists a very strong intramolecular steric interaction (H...H = 1.95 A) between the bridging and thioamide parts of the molecule, which makes such a form less stable. In the crystal structure of (Ia), intermolecular N-H...N and N-H...S hydrogen bonds link molecules into infinite tapes along the [1-10] direction. In (Ib), such intermolecular hydrogen bonds link molecules into infinite (101) planes. In (Ic), intermolecular N-H...N hydrogen bonds link molecules A and B into dimers, which are connected via N-H...S hydrogen bonds and form infinite chains along the c direction.

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Structure and nonlinear optical properties of phenylazo compounds. Structural characterization of 3-amino-3-morpholinyl-2-(o-nitrophenylazo)-propenonitrile and o-nitrophenylhydrazonomalononitrile

Cited by 7 publications

References 17 publications

Molecular Crystal Structures and Nonlinear Optical Properties in the Series of Dicyanovinylbenzene and Its Derivatives

Molecular Crystal Structures and Nonlinear Optical Properties in the Series of Dicyanovinylbenzene and Its Derivatives

Microwave-assisted preparation of 4-amino-3-cyano-5-methoxycarbonyl-N-arylpyrazoles as building blocks for the diversity-oriented synthesis of pyrazole-based polycyclic scaffolds

Polymorphism and solvolysis of 2-cyano-3-[4-(N,N-diethylamino)phenyl]prop-2-enethioamide

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