The Preparation of Nitro Compounds from Oximes. I<sup>1</sup>

Iffland, Don C.; Criner, G. X.; Koral, M.; Lotspeich, F. J.; Papanastassiou, Zinon B.; White, Steven

doi:10.1021/ja01112a048

Cited by 35 publications

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“…They were obtained from the corresponding bromonitroalkanes in only low yields of 28 and 20%, respectively, following the K2C03-procedure described for the preparation of 6 and 7. The physical data of 8 and 9 resembled those given in the literature [5].…”

Section: Preparation Of W-halonitroalkanesmentioning

confidence: 72%

“…-These compounds have all been described before. The most general method of preparing them is the bromination of cycloalkanone oximes with subsequent reductive debromination [5] (Eqn. 6 in Sec-[ion 3).…”

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confidence: 99%

“…Another unexpected observation that stimulated our interest was the spontaneous dimerization to 2 and 3 that occurred whenever we tried to generate 1-lithio-1-nitrocyclopropane (or the lithium salt of the corresponding mi-nitroalkane) and to combine it with electrophiles. Finally, 5 was one of the products of oxidation of the lithium salt or silyl ester [ 1 b] [2] of aci-nitrocyclopentane with lead tetraacetateh). 1.…”

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confidence: 99%

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Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

Kai

Knöchel

Kwiatkowski³

et al. 1982

Helvetica Chimica Acta

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Attempts to deprotonate nitrocyclopropane led to solutions which showed strong ESR. signals (Fig. 1)and from which 1‐nitro‐ l′‐nitroso‐bicyclopropyl (3) and 1,1′‐dinitro‐bicyclopropyl (2) were isolated. The activation energy for rotation about the central C, C‐bond of 2 is estimated to be about 12 kcal/mol (1 H‐NMR. spectra in Fig. 2). In contrast, the oven‐chain analogue 2,3‐dimethyl‐2,3‐dinitrobutane (1) shows a methyl singlet down to −70° C. Low‐temperature X‐ray analyses of 1, 2, 3, and also of 1,1′‐dinitro‐bicyclobutyl (4) show that all four molecules have gauche‐conformations but reveal striking structural differences between the openchain and the cyclic derivatives (Fig. 4–6): the central C, C‐bond is long in 1 (1.575 Å), short in 2 (1.479 Å); the C, N‐bonds are long in 1 (1.549 Å), short in 2 (1.488 Å); the orientation of the nitro groups is bisected in 2 and perpendicular in 1. The crystal structure of the nitro‐nitroso compound 3 is isomorphous with that of the dinitro compound 2 and thus disordered (Fig. 15–16). The effect of the nitro group as π‐electron acceptor on the molecular conformations and bond lengths is discussed. From analysis of the anisotropic vibrational parameters of 2 the root‐mean‐square librational amplitude of the nitro groups about their C, N‐bonds is estimated to be about 5.8° at 95 K, corresponding to a rotational barrier of about 9 kcal/mol, i. e. the same order of magnitude as the NMR. estimate of about 12 kcal/mol for C, C‐rotation.

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Section: Preparation Of W-halonitroalkanesmentioning

confidence: 72%

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confidence: 99%

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Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

Kai

Knöchel

Kwiatkowski³

et al. 1982

Helvetica Chimica Acta

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“…With the exception of III, such a "splitting" occurred in the In 10% behzene solution. 6 See Fig. 1 for spectrum.…”

Section: Resultsmentioning

confidence: 99%

A NUCLEAR MAGNETIC RESONANCE STUDY OF syn-anti ISOMERISM IN KETOXIMES

Lustig¹

1961

J. Phys. Chem.

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NUCLEsR 31AGNETIC RESONANCE O F Sy?Z-anti ISOMERISM IN KETOXIMES 49 1 of P(O), however, as it is reasonable to expect much of Ihe effects of correlation to cancel. In any case the entire polymer chain would collapse to within A' of the surface as P(0,t') for the polymer given by Fig. 2 approaches unity.A significant point with regard to equation 15 and the curves of Fig. 2 is that P(0) may bevery sensitive to 8 over a certain range of 8. In considering the thermodynamics of chain adsorption*J the number of anchoring segments v = P(O)t is an important factor. It is seen that for e going from 0 to 0.9, v may vary over a wide range (-a factor of ten) if, say K-10 a t 0 = 0 (or K-1 a t 8 = 0.9 if K O remains constant). Any isotherm equation should take this variation of v into account if agreement with experiments is to he expected. Comparison of Calculations with DataRecently Fontana and Thomas13 have carried out some very interesting experiments bearing on the problem of the configuration of adsorbed polymers. They were able to directly determine P(0) for poly-(alkyl methacrylate), PLMA, adsorbed onto silica by infrared spectrometry.Their investigation showed that, for this system, P(0) is relatively independent of 8 over a wide range of e. Since it is clear from their work that the mechanism of adsorption involves hydrogen bonding between the surface hydroxyl groups on (13) E. J. I'ontana and J. R. Thomas, J . Phys. Chem., 66, 480 (1961).the silica and the carbonyl groups on the polymer, e is very likely relatively large (>5kT) for this case. Thus, their data is consistent with the idea that this system is operating a t the upper regions of the curves in Fig. 2 where P(0) is relatively insensitive to 8.These investigators found, however, that the relatively constant value for P(0) was not unity but instead about 0.4. This, as the authors point out, most probably is a result of the combination of polymer backbone inflexibility and availability of properly spaced adsorption sites. It is to be expected that as P(0) approaches a value as high as 0.4 the chain becomes relatively rigid (as compared to the solution configuration) and surface site spacing and surface uniformity requirements become more critical. Furthermore, under these conditions both intermolecular and intramolecular overlapping of portions of the chains will lead to smaller P(0) because of steric effects. Alternatively it may be stated that at P(0) = 0.4 the entire PLMA chain is collapsed t o the surface to the extent that equation 18 might be more appropriate.Acknowledgments.-The author wishes to acknowledge the very helpful suggestions and discussions concerning the problem with Drs. 0. L. Isomerism of the syn-anti kind has been detected for the first time in several aliphatic ketoxinies and ketoxime ethers and is indicated by the presence of two resonance lines for the protons on carbon atoms next to the >C=KOH or >C=SOR group. The separation of these two lines depends on (a) the presence of aromatic compounds, acids or bases in the oxime solution, ...

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“…41 1 H NMR, δ: 1.66 (br.s, 8 H); 2.60, 2.84 (both dd, 2 H each, J = 15.5 Hz, J = 7.5 Hz). 13 C NMR, δ: 23.33, 28.09 (C(3), C(4)); 43.36 (C(2)); 99.67 (C(1)).…”

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Electrooxidative coupling of salts of nitro compounds with halide, nitrite, cyanide, and phenylsulfinate anions

et al. 2005

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Electrolysis of salts of primary and secondary nitro compounds (nitroethane, 1 and 2 nitropropanes, nitrocyclohexane, and nitrocycloheptane) in the presence of excess halide, nitrite, cyanide, and phenylsulfinate anions under undivided and divided amperostatic elec trolysis conditions in a two phase medium (CH 2 Cl 2 /H 2 O) produces geminal nitrohalides (35-85% yields), dinitro compounds (15-51%), nitronitriles (6-27%), and nitrosulfones (50-70%). The salts of secondary nitro compounds form the products of oxidative coupling with halide and phenylsulfinate anions under the undivided electrolysis conditions. In all other cases, divided electrolysis is required.

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The Preparation of Nitro Compounds from Oximes. I¹

Cited by 35 publications

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Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

A NUCLEAR MAGNETIC RESONANCE STUDY OF syn-anti ISOMERISM IN KETOXIMES

Electrooxidative coupling of salts of nitro compounds with halide, nitrite, cyanide, and phenylsulfinate anions

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The Preparation of Nitro Compounds from Oximes. I1

Cited by 35 publications

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Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives

A NUCLEAR MAGNETIC RESONANCE STUDY OF syn-anti ISOMERISM IN KETOXIMES

Electrooxidative coupling of salts of nitro compounds with halide, nitrite, cyanide, and phenylsulfinate anions

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The Preparation of Nitro Compounds from Oximes. I¹