Generation, Spectroscopy, and Structure of Cyanoformyl Chloride and Cyanoformyl Bromide, XC(O)CN

Pasinszki, Tibor; Vass, Gábor; Klapstein, Dieter; Westwood, N. P. C.

doi:10.1021/jp301528q

Cited by 7 publications

(4 citation statements)

References 43 publications

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“…It is well-known that the detailed analysis of band contours in infrared spectra can provide valuable information regarding the gas-phase structure of rotamers. − The experimentally observed band contours for CF 3 CH 2 SNO and CH 3 CH 2 SNO are also listed in Tables and . Calculated rotational constants (cm –1 ) and molecular parameters, together with the estimated separation between P and R branches [Δν(PR) values, in cm –1 ] as obtained following the classical method of Seth-Paul, are collected in Table .…”

Section: Resultsmentioning

confidence: 99%

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

et al. 2014

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The simple 2,2,2-trifluoroethyl thionitrite molecule, CF3CH2SNO, has been prepared in good yield for the first time using CF3CH2SH and NOCl in slight excess. The vapor pressure of the red-brown compound CF3CH2SNO follows, in the temperature range between 226 and 268 K, the equation log p = 12.0-3881/T (p/bar, T/K), and its extrapolated boiling point reaches 51 °C. Its structural and conformational properties have been compared with the ethyl thionitrite analogue, CH3CH2SNO. The FTIR spectra of the vapor of both thionitrites show the presence of bands with well-defined contours, allowing for a detailed conformational analysis and vibrational assignment on the basis of a normal coordinate analysis. The conformational space of both thionitrite derivatives has also been studied by using the DFT and MP2(full) level of theory with extended basis sets [6-311+G(2df) and cc-pVTZ]. The overall evaluation of the experimental and theoretical results suggests the existence of a mixture of two conformers at room temperature. The relative abundance of the most stable syn form (N═O double bond syn with respect to the C-S single bond) has been estimated to be ca. 79 and 75% for CF3CH2SNO and CH3CH2SNO, respectively.

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Section: Resultsmentioning

confidence: 99%

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

et al. 2014

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“…The cyanoformaldehyde “motif” appears in many related molecules where the carbonyl hydrogen is substituted for another atom or functional group. For example, cyanoformyl chlorides, acetyl cyanide, or carbonyl cyanide have all been studied as well as its sulfur-bearing analogue and isomers …”

Section: Introductionmentioning

confidence: 99%

“…The cyanoformaldehyde "motif" appears in many related molecules where the carbonyl hydrogen is substituted for another atom or functional group. For example, cyanoformyl chlorides, 6 acetyl cyanide, 7 or carbonyl cyanide 8 have all been studied as well as its sulfur-bearing analogue and isomers. 9 To the best of our knowledge, the whole family of cyanoformaldehyde isomers has not been studied systematically in any theoretical or experimental work.…”

Section: ■ Introductionmentioning

confidence: 99%

Structure and Spectroscopy of C₂HNO Isomers

2017

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Formyl cyanide has been detected toward Sgr B2 making this chemical and its potential isomers of astrophysical interest. We calculated the precise energies of the five most stable structural isomers of formyl cyanide and found that formyl isocyanide and 2H-azirin-2-one are less stable than formyl cyanide by 55 and 125 kJ/mol, respectively. We present our ab initio coupled cluster predictions of the spectroscopic parameters relevant to their gas-phase rotational and vibrational spectroscopy. Parameters include ground vibrational state rotational constants, centrifugal distortion parameters, equilibrium electric dipole moments, and nuclear quadrupole coupling constants. Anharmonic vibrational frequencies together with infrared intensities of fundamental and nonfundamental modes were also calculated. The broader potential energy surface, including transition states and the minima they connect, were explored for these isomers at the B3LYP/aug-cc-pVTZ level of theory. Formyl cyanide can dissociate in an exothermic reaction to form HCN and CO or in an endothermic reaction to form HNC and CO. The activation energies for both processes are close to 260 kJ/mol. The activation barrier for conversion of formyl cyanide into formyl isocyanide is ∼180 kJ/mol. The energetic barrier for the exothermic decomposition of formyl isocyanide into HNC and CO is ∼210 kJ/mol. The barrier for transformation of formyl isocyanide into formyl cyanide is ∼130 kJ/mol. Formyl isocyanide seems to be a stable chemical and could potentially survive in a dense molecular cloud if formed. These data are useful for future identification of members of this family of molecules in a laboratory or in space.

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“…Based on this molecular transformation, cyanoformamides could be formed via cyanoformyl chloride from the commercially available trichloroacetonitrile ( 1 ) by the B 12 derivative as a redox mediator at room temperature in the air using the electrochemical method. The cyanoformyl chloride has an impact on synthetic organic chemistry to transform various fine chemicals, and its spectroscopic or theoretical analysis has been investigated due to the unique chemical properties . Nevertheless, only a few studies have reported generating cyanoformyl chloride that requires very harsh reaction conditions by thermolysis or pyrolysis …”

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Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B₁₂ Derivative

et al. 2021

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The B 12 derivative, heptamethyl cobyrinate, -mediated electrochemical synthesis of cyanoformamides has been developed. Aerobic oxygenation of the carbon-centered radical initiated in situ generation of the reactive acyl chloride intermediate, which led to cyanoformamides in the presence of an amine. This one-pot and scalable synthetic method has been demonstrated with 41 examples up to 94% yields with 21 new compounds. The mechanism of electrolysis mediated by the B 12 derivative has been proposed based on the DFT calculations.C yanoformamides are important synthetic targets for versatile building blocks in the synthesis of lactams, 1 acrylonitriles, 2 tetrazoles, 3 unsymmetrical ketones, 4 substituted ureas, 5 carbamoyl amidoximes, 6 and pyrrole-2-carboxamide. 7 The structural motif of cyanoformamides is also found in antifouling compounds. 8 Initially, cyanoformamides were prepared using cyanogen, 9 potassium cyanide, 10 carbonyl cyanide, 11 dichlorosulfenyl chlorides, 12 isonitroso Meldrum's acid, 13 or tetracyanoethylene. 14 Various advanced methods have been reported in the past decade that aim to address the safely implications without using toxic reagents as cyano source, such as hypervalent iodine/NH 4 OAc (Scheme 1a), 15a phosphoryl trichloride (POCl 3 )/1-acyl-1-carbamoyl oximes (Scheme 1b), 15b trimethylsilyl cyanide (TMSCN)/carbamoyl imidazoles (Scheme 1c), 4,15c tert-butyl nitrite ( t BuONO)/ trifluoropropanamides (Scheme 1d), 15d CsF/N,N-disubstituted aminomalononitriles (Scheme 1e), 15e and dichloroimidazolidinedione (DCIDs)/1-acyl-1-carbamoyl oximes (Scheme 1f). 15f Considering the importance of cyanoformamides in organic synthesis, the development of further improved methods is desired.Therefore, we envisaged that the electroorganic synthesis may be applicable to cyanoformamides synthesis. Electroorganic synthesis has attracted attention in organic synthesis since it circumvents the use of chemical reductants and oxidants by using an electric current. 16 Recently, we developed the unique electrochemical molecular transformation of the trichlorinated methyl compound (R 1 -CCl 3 ) to form the amide in the presence of amine by the B 12 derivative (heptamethyl cobyrinate perchlorate, C1) in air (Scheme 1g). 17 The reactive acyl chloride should be formed as an intermediate from the R 1 -

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Generation, Spectroscopy, and Structure of Cyanoformyl Chloride and Cyanoformyl Bromide, XC(O)CN

Cited by 7 publications

References 43 publications

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

Structure and Spectroscopy of C₂HNO Isomers

Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B₁₂ Derivative

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Generation, Spectroscopy, and Structure of Cyanoformyl Chloride and Cyanoformyl Bromide, XC(O)CN

Cited by 7 publications

References 43 publications

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX3CH2SNO, X = H and F)

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX3CH2SNO, X = H and F)

Structure and Spectroscopy of C2HNO Isomers

Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B12 Derivative

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Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX₃CH₂SNO, X = H and F)

Structure and Spectroscopy of C₂HNO Isomers

Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B₁₂ Derivative