Chemische Reaktionen in Salzschmelzen XVI: Darstellung und Eigenschaften einiger Trifluoracetyl‐pseudohalogenide

Lidy, W.; Sundermeyer, W.

doi:10.1002/cber.19761090435

Cited by 32 publications

(11 citation statements)

References 15 publications

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“…This procedure affords-with good regio-and stereoselectivities-highly substituted acrylonitriles, which constitute building blocks for the synthesis of different compound classes such as lactones, amino acids, and dicarboxylic acid derivates. 14À17 In addition, some acyl cyanides such as CF 3 C(O)CN 18 are useful precursors of the carboxylic acids cyanide dimers, which also exhibit further applications in preparative chemistry. 19 Further examples of the high reactivity of carbonyl cyanides have also been reported in organometallic chemistry.…”

Section: ' Introductionmentioning

confidence: 99%

Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

et al. 2011

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The novel molecule difluorochloroacetyl cyanide, ClF(2)CC(O)CN, has been characterized by IR (gas phase, Ar matrix), Raman (liquid), (19)F and (13)C NMR, and photoelectron (PES) spectroscopies; photoionization mass spectrometry (PIMS); and gas electron diffraction (GED). The conformational properties of ClF(2)CC(O)CN have been studied by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. The existence of two conformers is detected in the gas and liquid phases, in which the C-Cl bond adopts gauche and syn orientations with respect to the C═O group. The computed enthalpy difference is in harmony with the experimental results of the gauche being more stable than the syn conformer by ΔH° = 1.3 kcal mol(-1) (MP2/cc-pVTZ). The valence electronic properties and the possible ionization and dissociation processes of the title compound are studied using the PES and PIMS. The experimental first vertical ionization energy of 12.0 eV corresponds to the ejection of an electron of the oxygen lone pairs. Taking into account the properties and broad applications of acyl cyanides, ClF(2)CC(O)CN is a promising new precursor in preparative chemistry.

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Section: ' Introductionmentioning

confidence: 99%

Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

et al. 2011

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“…N-Silylimines derived from electron-deficient carbonyl compounds can be obtained by an aza-Wittig-type reaction with triphenyl-N-(trimethylsilyl)phosphinimine. [64] Enolizable N-(trimethylsilyl)imines have been produced at low temperatures (-70 to -30 8C) as intermediates in â-lactam syntheses. [65] The reaction of acetaldehyde with lithium hexamethyldisilazanide in dry tetrahydrofuran-d 8 at -30 8C gives rise to the imine with a characteristic C=N IR absorption of 1680 cm -1 and the 1 H NMR signal of the vinylic proton at ä 8.50.…”

Section: Methods 5: From Nitrilesmentioning

confidence: 99%

Product Class 7: Imines

Padwa¹,

Bellus²

2005

Category 4. Compounds With Two Carbon Heteroatom Bonds

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Compounds with the general structure R 1 R 2 C=NR 3 , referred to as imines, were first obtained by Schiff via condensation of ketones and aldehydes with primary amines. Therefore, the condensation products are also called Schiff bases. In addition, the nominations azomethine, ketimine (derived from ketones), aldimine (derived from aldehydes), and anil (derived from anilines) are in use. It is recommended that the terms imine(s), ketimine(s), or aldimine(s) are used, rather than Schiff base(s) or azomethine(s).Since imines have to be considered as analogues of carbonyl compounds, many of the chemical properties are similar to the latter. Imines are used in new C-C bond formations, and reactions with electrophiles (e.g., aldehydes, alkyl halides), and the C=N moiety can undergo nucleophilic reactions. Generally, imines are very useful compounds in organic synthesis, as they are used in several syntheses of aza-heterocyclic compounds. Most imines are stable in an alkaline medium and therefore can be dried over potassium hydroxide. In diluted acid, however, they are easily hydrolyzed. In many cases intermediary imines cannot be isolated because of their lability. The presence of a C=N bond creates the possibility for E/Z isomerism (syn/anti). It has been recognized that such geomet-

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“…The related 1,1-dicyanoalquil carboxilato CH 3 C(O)OC(CN) 2 CH 3 has been used, for instance, to form the widely used vinylidene cyanide through the pyrolysis of the former compound. 1 In effect, during the synthesis of CClF 2 C(O)CN 2 4 has been also characterized in the present work. Very recently, benzoyl cyanide was reported to be ideally suited for quantitative, time-resolved analysis of RNA folding and ribonucleoprotein (RNP) assembly mechanisms.…”

Section: ■ Introductionmentioning

confidence: 98%

Dimers of Perhaloacetyl Cyanides: CClF₂C(O)OC(CN)₂CClF₂ and CF₃C(O)OC(CN) ₂CF₃. Preparation, Properties, and Spectroscopy

et al. 2014

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The vapor of the new compound 1,1-dicyano-2-chloro-2,2-difluoroethyl chlorodifluoroacetate, CClF2C(O)OC(CN)2CClF2 and of the known 1,1-dicyano-2,2,2-trifluoroethyl trifluoroacetate, CF3C(O)OC(CN)2CF3, were investigated using vibrational spectroscopy tools. The existence of rotational isomerism was confirmed for CClF2C(O)OC(CN)2CClF2 when the matrix isolated compound was examined in combination with the computational results applying quantum chemical models. From the four conformers gauche-syn-gauche, gauche-syn-anti, syn-syn-anti, syn-syn-gauche (the used nomenclature is with respect to the ϕ(ClC-C(O)), ϕ((O)C-OC), and ϕ(OC-CCl) torsion angles, respectively) predicted for CClF2C(O)OC(CN)2CClF2 the first two forms can be evidenced using Ar-matrix IR spectroscopy, with the first one being the most abundant at room temperature. On the other side, the results obtained for CF3C(O)OC(CN)2CF3 reveals the existence of only one syn-syn-anti form. CClF2C(O)OC(CN)2CClF2 melts at -40 °C and its vapor pressure was fitted by the equation ln p = -4732.6 (1/T) + 10.75 (p [Atm], T [K]) in the range -20 to 20 °C. Its extrapolated boiling point is 167 °C. The first ionization potentials occur for CClF2C(O)OC(CN)2CClF2 and CF3C(O)OC(CN)2CF3 at 12.13 and 12.43 eV, respectively, and were attributed to the ejection of electrons formally located at the carbonylic oxygen lone-pair electrons (nO). The proposed interpretation of the photoelectron spectrum is consistent with related molecules reported previously, and also with the prediction of Outer Valence Green's Functions (OVGF).

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Chemische Reaktionen in Salzschmelzen XVI: Darstellung und Eigenschaften einiger Trifluoracetyl‐pseudohalogenide

Cited by 32 publications

References 15 publications

Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Product Class 7: Imines

Dimers of Perhaloacetyl Cyanides: CClF₂C(O)OC(CN)₂CClF₂ and CF₃C(O)OC(CN) ₂CF₃. Preparation, Properties, and Spectroscopy

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Chemische Reaktionen in Salzschmelzen XVI: Darstellung und Eigenschaften einiger Trifluoracetyl‐pseudohalogenide

Cited by 32 publications

References 15 publications

Chlorodifluoroacetyl Cyanide, ClF2CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Chlorodifluoroacetyl Cyanide, ClF2CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Product Class 7: Imines

Dimers of Perhaloacetyl Cyanides: CClF2C(O)OC(CN)2CClF2 and CF3C(O)OC(CN) 2CF3. Preparation, Properties, and Spectroscopy

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Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Chlorodifluoroacetyl Cyanide, ClF₂CC(O)CN: Synthesis, Structure, and Spectroscopic Characterization

Dimers of Perhaloacetyl Cyanides: CClF₂C(O)OC(CN)₂CClF₂ and CF₃C(O)OC(CN) ₂CF₃. Preparation, Properties, and Spectroscopy