Methoxychlorocarbene.  Matrix spectroscopy and photochemistry

Kesselmayer, M. A.; Sheridan, Robert S.

doi:10.1021/ja00261a017

Cited by 49 publications

(19 citation statements)

References 8 publications

(16 reference statements)

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“…Also, methoxy- , and phenoxychlorocarbene were generated by laser flash photolysis, trapped in solid argon at 10 K, and characterized by matrix isolation IR and UV spectroscopy; both compounds will be studied on the magnetic criterion along Chapter 3.2 ( vide infra ). The 13 C chemical shifts of the carbene carbon atom in 12 and 13 have been already calculated using DFT [PBE0/6-311++G(2df,pd)] and the GAIO method [ 12 : δ( 13 C) = 541 ppm; 13 : δ( 13 C) = 304 ppm] …”

Section: Results and Discussionmentioning

confidence: 99%

Quantification of σ-Acceptor and π-Donor Stabilization in O, S and Hal Analogues of N-Heterocyclic Carbenes (NHCs) on the Magnetic Criterion

Kleinpeter

Koch

2021

J. Phys. Chem. A

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The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in 1 H NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes ↔ ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and 13 C chemical shifts of the electron-deficient carbon centers.

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Section: Results and Discussionmentioning

confidence: 99%

Quantification of σ-Acceptor and π-Donor Stabilization in O, S and Hal Analogues of N-Heterocyclic Carbenes (NHCs) on the Magnetic Criterion

Kleinpeter

Koch

2021

J. Phys. Chem. A

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“…It can also be synthesized using t-butyl hypochlo-rite as the chlorination agent (40, 41), but product prepared by that method cannot readily be freed of t-butanol and HCl. Acetoxyoxirane was conveniently prepared by epoxidation of vinyl acetate with dimethyldioxirane.…”

Section: Resultsmentioning

confidence: 99%

The Formamidopyrimidine Derivative of 7-(2-Oxoethyl)-2′-deoxyguanosine

Christov

Kozekov

Rizzo

et al. 2008

Chem. Res. Toxicol.

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Vinyl chloride induces hepatic angiosarcomas, which are otherwise rare malignancies. The biochemical basis involves the formation of the epoxide, which reacts with DNA to give ~98% of the 7-(2-oxoethyl) adduct (4) of dGuo plus small amounts of the etheno derivatives of dGuo, dCyd, and dAdo. The carcinogenicity is generally ascribed to the etheno adducts, not 4, because 4 has been shown to disappear from cells rapidly and to have negligible mutagenicity, which argues against its biological importance, whereas etheno adducts are both persistent and mutagenic. It has also been shown that apurinic sites derived from 4 are unlikely to be crucial lesions. A confounding factor with regard to the etheno hypothesis is that etheno adducts arise in unexposed cells by reactions of various lipid peroxidation products. The present study explores the possibility that a major contributor to the carcinogenicity of vinyl chloride may be formamidopyrimidine (FAPy) 12, N-[2-amino-6-[(2-deoxy-β-D-erythro-pentofuranosyl)amino]-3,4-dihydro-4-oxo-5-pyrimidinyl]-N-(2-oxoethyl)-formamide, which can arise by ring opening of 4, although its formation has not been observed until the present study. N7 adduct 4 undergoes deglycosylation to give 7-(2-oxoethyl)-Gua (13) in acid and imidazolium ring-opening to 12 in base. At pH 7.4, both processes occur with the formation of 12 representing ~10% of the product mixture. FAPy 12 spontaneously cyclizes to 22, which upon mild acid treatment yields the deglycosylation product 2-amino-3,4,7,8-tetrahydro-7-hydroxy-4-oxopteridine-5(6H)-carbaldehyde (14). The structure of 14 has been established by NMR and mass spectroscopy and by independent synthesis. Reaction of the epoxide of crotonaldehyde with dGuo failed to give either 13 or 14, indicating that both compounds are unique products of the reactions of dGuo with the epoxides of vinyl monomers. Although FAPy 12 was found to be unstable, carbinolamine 22 arising from cyclization of 12 may be an important contributor to the carcinogenicity of vinyl chloride.

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“…The ground states of : CBr 2 and : CI 2 have also been predicted to be singlet [157]. Chloromethoxy carbene, ClÐCÐOCH 3 , has been studied spectroscopically [158]. See also reference 159 for an experimental and theoretical study of : C(OCH 3 ) 2 and FÐCÐOCH 3 .…”

Section: Carbenesmentioning

confidence: 99%

Pericyclic Reactions

2000

Orbital Interaction Theory of Organic Chemistry

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Methoxychlorocarbene. Matrix spectroscopy and photochemistry

Cited by 49 publications

References 8 publications

Quantification of σ-Acceptor and π-Donor Stabilization in O, S and Hal Analogues of N-Heterocyclic Carbenes (NHCs) on the Magnetic Criterion

Quantification of σ-Acceptor and π-Donor Stabilization in O, S and Hal Analogues of N-Heterocyclic Carbenes (NHCs) on the Magnetic Criterion

The Formamidopyrimidine Derivative of 7-(2-Oxoethyl)-2′-deoxyguanosine

Pericyclic Reactions

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